WO2013031737A1 - ネガ型感光性樹脂組成物、隔壁および光学素子 - Google Patents

ネガ型感光性樹脂組成物、隔壁および光学素子 Download PDF

Info

Publication number
WO2013031737A1
WO2013031737A1 PCT/JP2012/071613 JP2012071613W WO2013031737A1 WO 2013031737 A1 WO2013031737 A1 WO 2013031737A1 JP 2012071613 W JP2012071613 W JP 2012071613W WO 2013031737 A1 WO2013031737 A1 WO 2013031737A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
photosensitive resin
resin composition
solvent
negative photosensitive
Prior art date
Application number
PCT/JP2012/071613
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
川島　正行
高橋　秀幸
古川　豊
光太郎 山田
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to JP2013531309A priority Critical patent/JP6136928B2/ja
Priority to CN201280042624.9A priority patent/CN103765314B/zh
Priority to KR1020147005137A priority patent/KR101923249B1/ko
Publication of WO2013031737A1 publication Critical patent/WO2013031737A1/ja

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

Definitions

  • the present invention relates to a negative photosensitive resin composition, a partition using the same, and an optical element having the partition.
  • a partition used for a pixel portion of a color filter or an organic EL (Electro-Luminescence) element, which is an optical element, is known by a method in which a photosensitive resin composition is applied to a substrate and formed by photolithography.
  • the partition wall is required to have a property of repelling ink containing water or an organic solvent which is an inkjet discharge liquid, so-called ink repellency.
  • ink repellency since the ink layer formed on the pixel by the inkjet method is required to have high film thickness uniformity, the opening (dot) surrounded by the partition wall has good wettability with respect to the discharge liquid. It is required to have so-called ink affinity.
  • Patent Document 1 discloses an ink repellent agent comprising a fluorine-containing hydrolyzed condensate that solves such a problem and has a sufficiently small surface free energy and can maintain ink repellency even after being subjected to ultraviolet / ozone irradiation treatment.
  • the technique of the negative photosensitive resin composition used for added partition formation is described.
  • Patent Document 1 when a photosensitive resin composition containing a fluorine-containing hydrolysis condensate is used, a highly polar solvent is used to stably hold the fluorine-containing hydrolysis condensate in the composition.
  • the solvents toluene: boiling point 111 ° C., 2-propanol: boiling point 82 ° C., diethylene glycol dimethyl ether: boiling point 162 ° C., propylene glycol monomethyl ether acetate: At a boiling point of 146 ° C., depending on the solvent composition and the amount of the solvent in the resin composition, agglomerated foreign matter of the fluorine-containing hydrolysis condensate may be generated at the time of drying, or the film after coating may be uneven. There was a problem.
  • the present invention relates to a negative photosensitive resin composition that has good ink repellency and can produce partition walls that can retain the ink repellency even after being subjected to ultraviolet / ozone irradiation treatment.
  • the present invention provides a negative photosensitive resin composition having a good coating property in which a film is formed and dried using this, the film thickness is uniform, there is no unevenness, and aggregates are not generated on the film surface.
  • the present invention has good ink repellency formed by curing the photosensitive resin composition, can retain the ink repellency even after being subjected to ultraviolet / ozone irradiation treatment, and has an appearance. It is an object of the present invention to provide a partition wall having a good and uniform film thickness and an optical element having the partition wall.
  • a negative photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C) and a solvent (D), wherein the ink repellent agent (C) is It consists of a fluorine-containing organosiloxane compound, and the solvent (D) contains a solvent (D1) having a boiling point of 165 to 210 ° C. in a proportion of 10 to 100% by mass with respect to the total amount of the solvent (D).
  • a negative photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C) and a solvent (D), wherein the ink repellent agent (C) is It consists of a fluorine-containing organosiloxane compound, and the solvent (D) contains a solvent (D1) having a boiling point of 165 to 210 ° C. in a proportion of 10 to 100% by mass with respect to the total amount of the
  • R F an organic group having a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms
  • R H an organic group having no perfluoroalkyl group
  • X hydrolyzable group
  • p 0, 1 or 2.
  • the solvent (D1) is a compound represented by the following formula (3).
  • R 1 O (C 2 H 4 O) y R 2 (3)
  • R 1 represents an alkyl group having 1 to 10 carbon atoms
  • R 2 represents an alkyl group having 2 to 10 carbon atoms
  • y represents an integer of 1 to 10.
  • the solvent (D) further contains a solvent (D2) having a hydroxyl group and a boiling point of less than 165 ° C. in a proportion of 1 to 50% by mass with respect to the total amount of the solvent (D).
  • Negative photosensitive resin composition according to any one of [1] to [5].
  • the composition further comprises a crosslinking agent (E), and the crosslinking agent (E) is a compound having two or more ethylenic double bonds in one molecule and having no acidic group.
  • a negative photosensitive resin composition capable of producing a partition wall having good ink repellency and capable of maintaining the ink repellency even after being subjected to ultraviolet / ozone irradiation treatment.
  • a negative photosensitive resin composition having a good coating property in which a coating film is formed and dried using this, the film thickness is uniform, there is no unevenness, and aggregates are not generated on the film surface.
  • the ink repellency formed by curing the photosensitive resin composition is good, and the ink repellency can be maintained even after the ultraviolet / ozone irradiation treatment.
  • a partition wall having a good appearance and a uniform film thickness and an optical element having the partition wall can be provided.
  • (meth) acryloyl ...” is a general term for “methacryloyl ...” and “acryloyl...”. The same applies to (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin.
  • the group represented by Formula (1) in this specification is called group (1).
  • the monomer represented by the formula (11) in this specification is referred to as a monomer (11).
  • the “side chain” in the present specification is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting a main chain in a polymer in which a repeating unit constitutes the main chain.
  • 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.
  • 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 “surface” of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the “surface” of the partition does not include the side surface of the partition.
  • the ink in the present specification is a general term for, for example, liquids having optically and electrically 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.
  • the ink repellency refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later. Embodiments of the present invention will be described below.
  • % 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
  • 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. Let react.
  • 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 polymer having a carboxy group is such that the carboxy group in the polymer becomes an acidic group after the reaction. The amount remaining in the 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.
  • z is an integer of 0 or 1 to 10.
  • the epoxy resin represented by the formulas (A1-2a) to (A1-2c) is reacted with a compound having a carboxy group and an ethylenic double bond and then reacted with a polyvalent carboxylic acid anhydride. It is preferable to use a mixture of a dicarboxylic acid anhydride and a tetracarboxylic dianhydride as the polyvalent carboxylic acid anhydride. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.
  • acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof are preferable, and acrylic acid or Methacrylic acid is particularly preferred.
  • 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, ZAR-2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H ( As described above, Nippon Kayaku Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation), Neopole 8430, 8473, 8475, 8478 (manufactured by Nippon Yupica), etc.
  • Examples of the monomer (A1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (NK ester CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the alkali-soluble resin (A) it is possible to obtain a high-resolution pattern by suppressing peeling of the cured film during development, the good linearity of the line, and the appearance after the post-baking process is maintained.
  • the resin (A1-2) is preferably used in 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 acidic group and ethylenic double bond introduced into novolac epoxy resin, Resin with acidic group and ethylenic double bond introduced into cresol novolac epoxy resin, Acid group and ethylene into trisphenol methane type epoxy resin Particularly preferred are resins in which an acidic double bond is introduced, and resins 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).
  • 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 exposed portion is excellent in curability, 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.
  • the photopolymerization initiator (B) in the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, but a compound that generates a radical by light is preferable.
  • Examples of the photopolymerization initiator (B) include ⁇ -diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.
  • Acylloin ethers thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone Thioxanthones such as 4-sulfonic acid; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Phenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4
  • 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 or a hydrogen atom in a cycloalkane ring.
  • 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.
  • R 3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in the benzene ring substituted with an alkyl group.
  • 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 20 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 12 carbon atoms.
  • R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom in which a hydrogen atom in the cycloalkane ring may be substituted with an alkyl group.
  • a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 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 Is a benzoyl group having 7 to 20 carbon atoms which 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, the number of carbon atoms
  • the photopolymerization initiator (4) include compounds (4-1) to (4) in which, in the formula (4), R 3 to R 9 are the following groups, and a indicating the number of R 0 is 0: (4-10).
  • Compound (4-1) 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, R 3 : methyl group, R 4 : octyl group, R 5 : ethyl group, R 6 , R 8 , R 9 : hydrogen atom, R 7 : benzoyl group (4-2), Compound (4-3) 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
  • a commercial item can be used for a photoinitiator (B).
  • Examples of 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone include IRGACURE 907 (trade name, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholino
  • Examples of phenyl) -butan-1-one include IRGACURE 369 (trade name, manufactured by BASF).
  • O-acyl oximes examples include IRGACURE OXE01 (manufactured by BASF, trade name: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)].) Adekaoptomer N-1919, Adeka Cruz NCI-831, NCI-930 (all manufactured by ADEKA, both trade names), and the like.
  • Examples of the photopolymerization initiator (4) include IRGACURE OXE02 (manufactured by BASF, trade name: corresponding to the above compound (4-7)) as a commercial product.
  • Examples of the photopolymerization initiator (4) examples include those described in International Publication No. 2008/078678. 1 to 71 can be used.
  • photopolymerization initiators (B) exemplified above, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferable because they may exhibit a sensitizing effect when used together with other radical initiators. .
  • the photopolymerization initiator (B) contained in the negative photosensitive resin composition may be one type or a mixture of two or more types.
  • the proportion of the photopolymerization initiator (B) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 5 to 15% by mass. Particularly preferred. Within the above range, the developability of the negative photosensitive resin composition is good.
  • the ink repellent agent (C) in the present invention comprises a fluorine-containing organosiloxane compound.
  • the fluorine-containing organosiloxane compound is preferably a compound having a fluorine atom content (hereinafter also referred to as fluorine atom content) of 10 to 55% by mass. 12 to 40% by mass is more preferable, and 15 to 30% by mass is particularly preferable. Within the above range, excellent ink repellency and ink repellency UV / ozone resistance can be imparted to the partition obtained from the negative photosensitive resin composition.
  • Examples of the fluorine-containing organosiloxane compound include compounds obtained by partial hydrolysis condensation of one or more hydrolyzable silane compounds including a hydrolyzable silane compound having a fluorine-containing organic group.
  • the partially hydrolyzed condensate of the hydrolyzable silane compound is usually a composition that itself has a molecular weight distribution.
  • the fluorine-containing organosiloxane compound as the ink repellent agent (C) in the negative photosensitive resin composition of the present invention is a partially hydrolyzed condensate of a hydrolyzable silane compound having such a fluorine-containing organic group. It is a liquid or solvent-soluble solid.
  • the fluorine-containing organosiloxane compound is preferably a partial hydrolysis condensate of a mixture containing the hydrolyzable silane compound (c-1) and the hydrolyzable silane compound (c-2) as essential components.
  • the hydrolyzable silane compound (c-1) and the hydrolyzable silane compound (c-2) are each partially hydrolyzed of the hydrolyzable silane compound (c-1).
  • Condensates and partially hydrolyzed condensates of hydrolyzable silane compounds (c-2) can also be used.
  • the hydrolyzable silane compound (c-1) is a compound represented by the following formula (c-1) (hereinafter also referred to as compound (c-1)).
  • R F an organic group having a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms
  • X Hydrolyzable group.
  • three Xs present in the compound may be different from each other or the same.
  • the compound (c-1) one type may be used alone, or two or more types may be used in combination.
  • a cured film obtained by curing the negative photosensitive resin composition can exhibit water repellency and oil repellency (that is, ink repellency).
  • the hydrolyzable silane compound (c-2) is a compound represented by the following formula (c-2) (hereinafter also referred to as compound (c-2)).
  • R H an organic group having no perfluoroalkyl group
  • X hydrolyzable group
  • p 0, 1 or 2.
  • the compound (c-2) is preferably a tetrafunctional compound in which p is 0, or a trifunctional compound in which p is 1.
  • the compound (c-2) one type may be used alone, or two or more types may be used in combination. When using 2 or more types together, a bifunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.
  • the ink repellent agent (C) is easily dissolved in a hydrocarbon solvent, which is compared with the case where a negative photosensitive resin composition coating film is formed on the surface of the substrate. Inexpensive solvents can be selected.
  • the group R F and the group R H in the ink repellent agent (C) used in the present invention are groups that exhibit water repellency, and oil repellency is mainly expressed by the group R F.
  • the presence of the group RH to some extent makes the ink repellent agent (C) easily dissolved in a hydrocarbon solvent, and the negative photosensitive resin composition is applied to the surface of the substrate.
  • a relatively inexpensive solvent can be selected when forming the film.
  • the fluorine-containing organosiloxane compound used in the present invention includes hydrolyzable silane compounds other than the compound (c-1) and the compound (c-2) in addition to the compound (c-1) and the compound (c-2). It may be a partially hydrolyzed condensate of a mixture containing Examples of hydrolyzable silane compounds other than the compound (c-1) and the compound (c-2) include monofunctional silane compounds, cyclic organopolysiloxanes, and hydrolyzates having functional group-containing organic groups called silane coupling agents. And decomposable silane compounds (excluding compounds (c-1) and (c-2)).
  • Examples of the monofunctional silane compound include the following hydrolyzable silane compound (c-3) having one hydrolyzable group and the following organodisiloxane (c-4). Furthermore, a hydrolyzable silane compound having an organic group having a polymerizable functional group can also be used as the hydrolyzable silane compound.
  • the organic group having a polymerizable functional group is preferably an organic group having at least one polymerizable functional group selected from an acryloyl group and a methacryloyl group.
  • a compound (c-2) in which at least one RH is an organic group having a polymerizable functional group, a monofunctional silane compound having an organic group having a polymerizable functional group, or the like can be used.
  • the compound (c-2) in which at least one of RH is an organic group having a polymerizable functional group the following hydrolyzable silane compound (c-5) is preferable.
  • the compound (c-2) is other than the hydrolyzable silane compound (c-5). It shall be said.
  • the hydrolyzable silane compound (c-3) is a monofunctional hydrolyzable silane compound in which three organic groups and one hydrolyzable group are bonded to a silicon atom.
  • a hydrolyzable silane compound represented by the following formula (c-3) (hereinafter also referred to as compound (c-3)) is preferred.
  • W represents an organic group having at least one polymerizable functional group selected from an acryloyl group and a methacryloyl group, the above R F or the above R H.
  • two R H three R H when W is R H ) may be the same as or different from each other.
  • the fluorine-containing organosiloxane compound used in the present invention in addition to the hydrolyzable silane compound, the following organodisiloxane (c-4), octamethylcyclotetrasiloxane which can be a monofunctional siloxane unit such as hexamethyldisiloxane. It may be a partially hydrolyzed condensate of a mixture containing a cyclic organopolysiloxane.
  • the organodisiloxane (c-4) is preferably an organodisiloxane represented by the following formula (c-4) (hereinafter also referred to as compound (c-4)). These are silane compounds capable of producing monofunctional siloxane units.
  • R H in the formula (c-4) is the same as R H in the formula (c-2).
  • W represents an organic group having at least one polymerizable functional group selected from an acryloyl group and a methacryloyl group, the above R F or the above R H.
  • W may be the same as or different from each other.
  • four R H (5 or 6 R H when W is R H ) may be the same as or different from each other.
  • W of the compound is R F , the relative proportion of the group R F of the ink repellent agent (C) is increased, and excellent oil repellency is exhibited.
  • W is preferably RH because the solubility of the ink repellent agent (C) in a hydrocarbon solvent is improved. It is preferable that W is an organic group having an acryloyl group or a methacryloyl group, since the curability of the ink repellent agent (C) is improved and the solubility in a hydrocarbon solvent is improved.
  • the hydrolyzable silane compound (c-5) has an organic group having at least one polymerizable functional group selected from the group consisting of q (q is 1 or 2) acryloyl group or methacryloyl group on a silicon atom.
  • q is 1 or 2
  • r is 0 or 1
  • q + r is 1 or 2.
  • the hydrolyzable silane compound (c-5) is preferably a hydrolyzable silane compound represented by the following formula (c-5) (hereinafter also referred to as compound (c-5)).
  • RH in the compound (c-5) is the same as X and R H in the formula (c-1) and (c-2).
  • RH in the compound (c-5) is a group other than Q.
  • Q represents an organic group having an acryloyl group or a methacryloyl group.
  • q is 1 or 2
  • r is 0 or 1
  • q + r is 1 or 2.
  • two Qs may be the same or different from each other.
  • q is preferably 1 and r is 1, or q is 1 and r is 0.
  • compound (c-5) one kind can be used alone, or two or more kinds can be used in combination.
  • the obtained ink repellent agent (C) is likely to stay on the upper surface of the partition wall after exposure, and has an effect of making the upper surface of the partition wall ink repellent and making the side wall surface of the partition wall ink-philic.
  • the ink repellent agent (C) is likely to move to the side surface of the partition after exposure, so that both the top surface and the side surface of the partition have an ink repellency.
  • the fluorine-containing organosiloxane compound is preferably a partially hydrolyzed condensate obtained by using the compound (c-5) as a part of the compound (c-2). Further, a partial hydrolysis condensate obtained by using the compound (c-3) is preferred so that the molecular weight of the fluorine-containing organosiloxane compound which is a partial hydrolysis condensate does not become too high.
  • a partial hydrolysis condensate obtained by partial hydrolysis condensation of a plurality of each compound in advance is used as necessary. It may be used.
  • partial hydrolytic condensation of compound (c-1) may be used instead of compound (c-1)
  • partial hydrolytic condensation of compound (c-2) may be used instead of compound (c-2).
  • X included in the compounds (c-1) to (c-5) include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which hydrogen of the amino group is substituted with an alkyl group.
  • X is preferably an alkoxy group having 4 or less carbon atoms or a halogen atom, particularly preferably CH 3 O—, C 2 H 5 O—, or Cl—.
  • a hydroxyl group sianol group
  • a hydrolysis reaction and further a reaction between molecules facilitates a Si—O—Si bonding reaction to proceed smoothly.
  • R F1 represents a perfluoroalkyl group that may contain an etheric oxygen atom having 3 to 10 carbon atoms
  • Y represents a divalent linking group containing no fluorine atom.
  • R F1 is preferably a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoroalkyl group containing an etheric oxygen atom having 4 to 9 carbon atoms, particularly preferably a perfluoroalkyl group having 6 carbon atoms.
  • the partition formed using the negative photosensitive resin composition exhibits excellent ink repellency and ink repellency of UV / ozone resistance, and can be applied to a general-purpose solvent. It is preferable because of its excellent solubility.
  • Examples of the structure of R F1 include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, and a linear structure is preferable.
  • R F1 include the following groups. F (CF 2 ) 4 —, F (CF 2 ) 6 —, F (CF 2 ) 8 —. CF 3 CF 2 OCF 2 CF 2 OCF 2 —, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 —, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 —, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 —, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 —.
  • Y is not particularly limited as long as it is a divalent linking group, - (CH 2) g - , - CH 2 O (CH 2) g -, - SO 2 NR 2 - (CH 2) g -, - ( A group represented by C ⁇ O) —NR 2 — (CH 2 ) g — is preferred.
  • g represents an integer of 1 to 5
  • R 2 represents a hydrogen atom, a methyl group, or an ethyl group.
  • Y is particularly preferably — (CH 2 ) g — where g is 2 or 3.
  • the direction of the group Y means that Si is bonded to the right side and R F1 is bonded to the left side.
  • Y is preferably a group represented by — (CH 2 ) g —.
  • g is preferably an integer of 2 to 4, and — (CH 2 ) 2 — in which g is 2 is particularly preferable.
  • R F1 is a perfluoroalkyl group containing an etheric oxygen atom having 4 to 9 carbon atoms
  • Y represents — (CH 2 ) h —, —CH 2 O (CH 2 ) h —, —SO 2
  • a group represented by NR 2 — (CH 2 ) h —, — (C ⁇ O) —NR 2 — (CH 2 ) h — is preferred.
  • h represents an integer of 1 to 5
  • R 2 represents a hydrogen atom, a methyl group, or an ethyl group.
  • Y is particularly preferably — (CH 2 ) 2 — in which h is 2.
  • the direction of bonding of the group Y means that Si is bonded to the right side and R F1 is bonded to the left side.
  • R H possessed by the compound (c-2), the compound (c-3), the compound (c-4) and the compound (c-5) has 1 to 4 carbon atoms except when it is Q.
  • Q of the compound (c-5) a group represented by Q 1 -Z- is preferable.
  • Q 1 represents a (meth) acryloyloxy group.
  • Z represents — (CH 2 ) 3 —, — (CH 2 ) 4 —, — (CH 2 ) 5 —, or — (CH 2 ) 6 —, and — (CH 2 ) 3 — is preferred.
  • the same group is preferable as the polymerizable functional group selected from the group consisting of acryloyl group and methacryloyl group optionally contained in compound (c-3) and compound (c-4).
  • the following examples are preferable. Si (OCH 3 ) 4 , Si (OCH 2 CH 3 ) 4 , CH 3 Si (OCH 3 ) 3 , CH 3 Si (OCH 2 CH 3 ) 3 , CH 3 CH 2 Si (OCH 3 ) 3 , CH 3 CH 2 Si (OCH 2 CH 3 ) 3 , (CH 3 ) 2 Si (OCH 3 ) 2 , (CH 3 ) 2 Si (OCH 2 CH 3 ) 2 ,
  • the following examples are preferred as specific examples of the partial hydrolysis-condensation product of compound (c-2) that can be used in place of compound (c-2).
  • a compound obtained by hydrolytic condensation of Si (OCH 3 ) 4 for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.
  • Compounds obtained by hydrolytic condensation of Si (OCH 2 CH 3 ) 4 for example, ethyl silicate 40 and ethyl silicate 48 (both trade names) manufactured by Colcoat).
  • the following examples are preferable.
  • the compound (c-4) the following examples are preferable.
  • CH 2 C (CH 3) COO (CH 2) 3 Si (OCH 3) 3
  • CH 2 C (CH 3) COO (CH 2) 3 Si (OCH 2 CH 3) 3
  • CH 2 CHCOO (CH 2) 3 Si (OCH 3) 3
  • CH 2 CHCOO (CH 2) 3 Si (OCH 2 CH 3) 3
  • [CH 2 C (CH 3 ) COO (CH 2) 3] CH 3 Si (OCH 3) 2
  • [CH 2 C (CH 3 ) COO (CH 2) 3] CH 3 Si (OCH 3) 2
  • [CH 2 C (CH 3 ) COO (CH 2) 3] CH 3 Si (OCH 2 CH 3) 2.
  • the ink repellent agent (C) is a reaction product obtained by reacting a mixture of the above compounds. This reaction is the production
  • Partially hydrolyzed condensates of bifunctional to tetrafunctional (especially trifunctional or tetrafunctional) hydrolyzable silane compounds of compounds (c-1), compounds (c-2), and compounds (c-5) and mixtures thereof Usually has a silanol group.
  • a partially hydrolyzed condensate is produced by co-condensing a bifunctional to tetrafunctional hydrolyzable silane compound together with a monofunctional silane compound (compound (3) or compound (4)), the silanol group is monofunctional.
  • the silanol group is lost by reacting with the functional silane compound, and the extension reaction of the siloxane chain due to the reaction between the silanol groups is stopped, so that the partial hydrolysis-condensation product with a small number of silanol groups per silicon atom and the molecular weight A low partial hydrolysis condensate is formed.
  • the ink repellent agent (C) may be a partially hydrolyzed condensate having a small number of silanol groups per silicon atom, or a partially hydrolyzed condensate having a relatively large number of silanol groups per silicon atom. Also good. In the latter case, the average number of silanol groups per silicon atom is preferably 0.2 to 3.5.
  • the cocondensation ratio of the compound (c-1) and the compound (c-2) is as described above.
  • it is not particularly limited as long as the fluorine atom content can be obtained it is preferable to use 0.1 to 9 mol of compound (c-2) with respect to 1 mol of compound (c-1). It is particularly preferable to use 0.5 to 9 mol.
  • the partially hydrolyzed condensate is converted into a compound having one silicon atom. In conversion, the co-condensation ratio is assumed. The same applies to the following cocondensation ratios.
  • Ink repellent agent (C) is added to compound (c-1) and compound (c-2) to form monofunctional siloxane units such as compound (c-3) and / or compound (c-4)
  • the cocondensation ratio of the total amount of compound (c-3) and compound (c-4) to the total amount of compound (c-1) and compound (c-2) is 300 mol% or less is preferable, 200 mol% or less is more preferable, and 100 mol% or less is particularly preferable.
  • the calculation of the co-condensation ratio is based on compound (c-3), and compound (c-4)
  • the molar amount is doubled and regarded as the molar amount of compound (c-3).
  • the copolymerization ratio calculated from the actual amount of compound (c-4) used is preferably 150 mol% or less, more preferably 100 mol% or less, A mol% or less is particularly preferred.
  • the compound (c-1) and the compound (c-2) Is preferably 500 mol% or less, particularly preferably 400 mol% or less.
  • the compound The cocondensation ratio of compound (c-3) with respect to the total amount of (c-1) and compound (c-2) is preferably 300 mol% or less, and the cocondensation ratio of compound (c-5) is 500 mol% or less.
  • the cocondensation ratio of the compound (c-3) with respect to the total amount of the compound (c-1) and the compound (c-2) is 200 mol% or less, and the cocondensation ratio of the compound (c-5) is It is 400 mol% or less.
  • the ink repellent agent (C) in the present invention may be composed of a single compound, but is usually a mixture composed of a plurality of compounds having different degrees of polymerization. That is, the ink repellent agent (C) is prepared using the compound (c-1) and the compound (c-2) as essential components and optionally using the compound (c-3) and / or the compound (c-4). In this case, an agent having the structure of the average composition formula represented by the following formula (1) is obtained.
  • the average composition formula represented by the formula (1) is a chemical formula when it is assumed that all of the hydrolyzable groups or silanol groups are siloxane bonds in the partially hydrolyzed condensate produced as described above.
  • R F , R H , W, and p are the same as described above.
  • m and n are each an integer of 1 or more, and k is 0 or an integer of 1 or more.
  • the value of k is preferably (m + n): k as an average value of the entire ink repellent agent (C), and k is preferably 3 or less with respect to 1 in the above range, that is, (m + n). It is particularly preferred that
  • the ink repellent agent (C) When the ink repellent agent (C) is produced using the compound (c-1) and the compound (c-2) as essential components and optionally using the compound (c-5), the following formula (2) It becomes an agent which has the structure of the average composition formula represented. However, since it is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or silanol group remains, it is difficult to express this product by a chemical formula, and the average composition formula represented by formula (2) Is a chemical formula assuming that all of the hydrolyzable groups or silanol groups are siloxane bonds in the partially hydrolyzed condensate produced as described above.
  • R F , R H , Q, and preferred ranges of p, q, and r are the same as described above.
  • Each of s and t is an integer of 1 or more, and u is 0 or an integer of 1 or more.
  • the compound (c-1) and the compound (c— 2) It is presumed that the units derived from the compound (c-5) optionally blended are randomly arranged. However, for example, when a partially hydrolyzed condensate of compound (c-2) is used instead of compound (c-2), the units derived from compound (c-2) are arranged in blocks. Guessed.
  • the values of s and t are within the above-mentioned range as the average value of the entire ink repellent agent (C), and s: t is the co-condensation ratio of compound (c-2) to compound (c-1), respectively. Preferably there is.
  • the value of u is preferably (s + t): u as an average value of the entire ink repellent agent (C), and u is preferably 5 or less with respect to 1 in the above range, that is, (s + t). It is particularly preferred that
  • (1) has a structure of an average composition formula in which units derived from the compound (c5) of the formula (2) are further co-condensed.
  • the above-mentioned range is mentioned as a cocondensation ratio of each compound.
  • the number average molecular weight (Mn) of the ink repellent agent (C) in the present invention is preferably 500 or more, preferably less than 1,000,000, more preferably less than 10,000, and particularly preferably less than 5,000.
  • the number average molecular weight (Mn) is not less than the lower limit, there is an advantage that evaporation from the substrate surface can be prevented when forming the partition using the negative photosensitive resin composition, and the number average molecular weight (Mn) Is less than the upper limit, the solubility in a solvent is improved, and there is an advantage that workability is improved.
  • the number average molecular weight (Mn) of the ink repellent agent (C) can be adjusted by selecting reaction conditions and the like.
  • the ink repellent agent (C) comprising a fluorine-containing organosiloxane compound can be produced by subjecting a mixture containing the hydrolyzable silane compound to hydrolysis and condensation reactions.
  • the reaction conditions usually used in the reaction for hydrolyzing and condensing the hydrolyzable silane compound can be applied to the reaction without any particular limitation.
  • it is preferable to use a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or an organic acid such as acetic acid, oxalic acid or maleic acid as a catalyst.
  • the amount of the catalyst used is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 1% by mass, based on the total amount of the mixture containing the hydrolyzable silane compound.
  • a solvent may be used for the reaction.
  • the solvent include water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, ethylene glycol, glycerin, and propylene glycol; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Cellsolves such as 2-methoxyethanol and 2-ethoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2 -Carbitols such as butoxyethoxy) ethanol; Esters such as methyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, 4-butyrolactone, butyl acetate, 3-methoxybutyl acetate; Glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glyco
  • a solvent may be used individually by 1 type, or may use 2 or more types together.
  • the solvent is blended in the negative photosensitive resin composition of the present invention in the form of an ink repellent solution.
  • the content ratio of the ink repellent agent (C) in the negative photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass, preferably 0.1 to 10% by mass in the total solid content in the negative photosensitive resin composition. 6 mass% is more preferred, and 0.5-3 mass% is particularly preferred.
  • the negative photosensitive resin composition of the present invention contains a solvent (D).
  • the solvent (D) contains the solvent (D1) having a boiling point of 165 to 210 ° C. in a proportion of 10 to 100% by mass with respect to the total amount of the solvent (D).
  • the solvent (D) reacts with the alkali-soluble resin (A) contained in the negative photosensitive resin composition, the photopolymerization initiator (B), the ink repellent agent (C), and optional components contained as necessary. And has a function of uniformly and simply applying the negative photosensitive resin composition to the substrate on which the partition walls are formed by uniformly dissolving or dispersing these solid components.
  • the ink repellent agent (C) has a function of facilitating transfer to the film surface.
  • the ink repellent agent (C) has a small surface free energy and high surface migration ability due to the fluorine-containing organosiloxane compound, but the boiling point is different depending on the solvent to be combined.
  • the solvent (D) containing the solvent (D1) at 165 ° C. or higher high surface migration is expressed. That is, by adjusting the boiling point of the solvent (D1) to 165 ° C. or higher, the drying speed of the negative photosensitive resin composition is adjusted to be sufficiently slow, and the ink repellent agent (C) moves to the film surface. I was able to secure time.
  • the fall of productivity and the fall of the reliability by a residual solvent are prevented by making the boiling point of a solvent (D1) into 210 degrees C or less.
  • the boiling point is 165 to 210 ° C, preferably 170 to 200 ° C.
  • the ink repellent agent (C) can have sufficient time for surface migration as described above, so that the ink repellent layer in the film of the negative photosensitive resin composition can be secured.
  • the thickness of the agent layer can be increased, and the ink repellency on the partition wall surface is improved.
  • the ink repellent agent (C) aggregates and precipitates when the ink repellent agent (C) moves to the surface, and an aggregate is generated. Since the surface transition time of C) can be sufficiently secured, the generation of this aggregate can be prevented. Furthermore, it is possible to prevent the problem of unevenness of the film appearance and non-uniformity of the film thickness that occurs when drying is completed without taking a sufficient leveling period because the drying speed of the coating film is too high.
  • the boiling point of the solvent (D1) is less than or equal to the upper limit of the above range, productivity does not decrease due to the occurrence of sticking or an increase in the time required for the drying step. It is possible to prevent influences such as a decrease in reliability due to peeling of a cured film at the time of development that occurs due to the remaining solvent, generation of outgas due to reheating after the formation of partition walls, and the like.
  • the content of the solvent (D1) in the solvent (D) is 10 to 100% by mass, preferably 20 to 80% by mass, particularly preferably 30 to 70% by mass.
  • the content is in the above range, in the coating and drying process of the negative photosensitive resin composition on the substrate surface, the film thickness is uniform and uniform, and a good film that does not generate aggregates on the film surface is obtained.
  • the repulsive force is exerted between the ink repellent agent (C) and the other solid components for a long time, so that the surface of the ink repellent agent (C) can be sufficiently transferred.
  • the thickness can be increased, and the ink repellency of the partition obtained is good.
  • solvent (D1) examples include diethylene glycol ethyl methyl ether (EDM, boiling point 176 ° C.), diethylene glycol diethyl ether (EDE, boiling point: 189 ° C.), diethylene glycol isopropyl methyl ether (IPDM, boiling point: 179 ° C.), propylene glycol diester.
  • EDM diethylene glycol ethyl methyl ether
  • EEE diethylene glycol diethyl ether
  • IPDM diethylene glycol isopropyl methyl ether
  • Acetate (boiling point: 190 ° C), propylene glycol n-butyl ether (boiling point: 170 ° C), 3-methoxybutyl acetate (boiling point: 171 ° C), 3-methoxy-3-methylbutyl acetate (boiling point: 188 ° C), dipropylene Examples include glycol dimethyl ether (boiling point: 175 ° C.), ethyl 3-ethoxypropionate (boiling point: 170 ° C.), 4-butyrolactone (boiling point: 204 ° C.), cyclohexanol acetate (boiling point: 173 ° C.), and the like. These may be used alone or in combination of two or more.
  • a compound represented by the following formula (3) is particularly preferable. Since the compound (3) contains polar etheric oxygen, it has a high ability to dissolve the ink repellent agent (C) and is excellent in storage stability.
  • R 1 represents an alkyl group having 1 to 10 carbon atoms
  • R 2 represents an alkyl group having 2 to 10 carbon atoms
  • y represents an integer of 1 to 10.
  • R 1 is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 carbon atom.
  • R 2 is preferably an alkyl group having 2 to 4 carbon atoms, particularly preferably an alkyl group having 2 carbon atoms.
  • y is preferably 1 to 3, and 2 is particularly preferable.
  • the compound (3) preferably used as the solvent (D1) are shown below together with their abbreviations and boiling points.
  • Examples include diethylene glycol ethyl methyl ether (EDM, boiling point: 176 ° C.), diethylene glycol diethyl ether (EDE, boiling point: 189 ° C.), diethylene glycol isopropyl methyl ether (IPDM, boiling point: 179 ° C.), and the like. These may be used alone or in combination of two or more. Of these, diethylene glycol ethyl methyl ether is particularly preferable.
  • the negative photosensitive resin composition of the present invention preferably uses a solvent (D2) in combination with a solvent (D1) as a solvent (D).
  • the solvent (D2) is a compound having a hydroxyl group in the molecule and having a boiling point of less than 165 ° C., and preferably has a viscosity at 25 ° C. of 2 mPa ⁇ s or less.
  • the ink repellent agent (C) is a partially hydrolyzed condensate, silanol groups remain in the product. Therefore, by including the solvent (D2) having the same hydroxyl structure as the silanol group in the negative photosensitive resin composition, the dispersion state of the ink repellent agent (C) in the composition is further stabilized by solvation. As a result, the storage stability of the negative photosensitive resin composition can be improved. On the other hand, since the solvent (D2) has a hydroxyl group, the viscosity is likely to increase due to hydrogen bonding between molecules as compared with a compound having the same molecular weight without a hydroxyl group.
  • the viscosity will be generally below the above upper limit, the substrate surface will have good wetting and spreading during coating, a large amount of liquid is required, and in-plane uniformity is There is no deterioration or unevenness.
  • the solvent (D2) specifically, propylene glycol monomethyl ether (PGME, boiling point: 120 ° C., viscosity: 1.71 mPa ⁇ s (25 ° C.)), water (boiling point: 100 ° C., viscosity: 0.89 mPa ⁇ s) (25 ° C.)), 2-propanol (IPA, boiling point: 82 ° C., viscosity: 1.96 mPa ⁇ s (25 ° C.)), and the like.
  • the ratio of the solvent (D2) to the total amount of the solvent (D) is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass.
  • 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 solvent used in the synthesis of the alkali-soluble resin (A) or the ink repellent agent (C), or the like, together with the alkali-soluble resin (A) or the ink repellent agent (C), the negative photosensitive resin composition. Examples of the solvent used when blended with products.
  • the said solvent (D1) and a solvent (D2) may be used as a solvent used for the synthesis
  • the said solvent (D1) and a solvent (D2) may be used as a solvent used for the synthesis
  • the said solvent (D1) and a solvent (D2) may be used as a solvent used for the synthesis
  • combination of the said alkali-soluble resin (A) or an ink repellent agent (C) the said solvent (D1) and a 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,
  • the solvent (D3) include diethylene glycol dimethyl ether (MDM, boiling point: 162 ° C.), propylene glycol 1-monomethyl ether 2-acetate (PGMEA, boiling point: 146 ° C.), diethylene glycol monoethyl ether acetate (EDGAC, boiling point: 217). ° C), butyl acetate (boiling point: 126 ° C), cyclohexanone (boiling point: 156 ° C), solvent naphtha (boiling point: 150-200 ° C), and the like.
  • Solvent naphtha is a mixed solvent of petroleum compounds, and as its boiling point indicates, the composition includes a compound classified as solvent (D1). In the present specification, the solvent having a boiling point exceeding the boiling point of the solvent (D1) is classified as the solvent (D3).
  • the content of the solvent (D3) in the solvent (D) is an amount obtained by subtracting the amounts of the solvent (D1) and the solvent (D2) from the total amount of the solvent (D), specifically, the total amount of the solvent (D).
  • the content is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass.
  • an aspect configured by the solvent (D1), the solvent (D2), and / or the solvent (D3), which is configured only by the solvent (D1) can be given.
  • solvent (D1): solvent (D2): solvent (D3) ) 50 to 90: 5 to 45: 5 to 45.
  • the content of the solvent (D) in the negative photosensitive resin composition varies depending on the composition and use of the negative photosensitive resin composition, but is 50 to 99% by mass in the negative photosensitive resin composition. It is preferably blended, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.
  • the negative photosensitive resin composition of the present invention may contain a crosslinking agent (E) as an optional component that promotes radical curing.
  • a crosslinking agent (E) a compound having two or more ethylenic double bonds in one molecule and having no acidic group is preferable.
  • crosslinking agent (E) 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 urethane acrylate and the like.
  • urethane acrylate from the viewpoint of photoreactivity, it is preferable to have a large number of ethylenic double bonds.
  • pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated isocyanuric acid triacrylate, and urethane acrylate are preferable.
  • these may be used individually by 1 type, or may use 2 or more types together.
  • crosslinking agent (E) Commercial products can be used as the crosslinking agent (E).
  • 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 ester 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 Petro
  • 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.
  • KAYARAD DPHA and NK ester A-9530 are preferable because they improve the sensitivity of the cured film obtained from the negative photosensitive resin composition.
  • NK esters A-9300, BANI-M and BANI-X are preferred from the viewpoint of imparting hardness to the cured film and suppressing thermal sagging.
  • NK ester A-9300-1CL is preferable from the viewpoint of imparting flexibility to the cured film.
  • Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.
  • the content of the crosslinking agent (E) in the total solid content in the negative photosensitive resin composition is preferably 10 to 60% by mass, particularly preferably 20 to 55% by mass. When it is in the above range, the storage stability of the negative photosensitive resin composition becomes good, and when the patterned substrate obtained using the negative photosensitive resin composition is formed, the ink-jet ink in the pixel becomes wet. Property is improved.
  • the negative photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C), and a solvent (D). Furthermore, a crosslinking agent (E) is contained as needed. Further, the following thermal crosslinking agent (F), colorant (G), polymer dispersant (H), dispersion aid (I), silane coupling agent (J), fine particles (K), phosphoric acid compound (L ) And other additives.
  • the thermal crosslinking agent (F) in the present invention is a compound having two or more groups capable of reacting with a carboxy group and / or a hydroxyl group.
  • the thermal crosslinking agent (F) reacts with the alkali-soluble resin (A) to increase the crosslinking density of the cured film and improve the heat resistance.
  • thermal cross-linking agent (F) include at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds. These compounds may be used alone or in combination of two or more.
  • the content of the thermal crosslinking agent (F) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass. The developability of the negative photosensitive resin composition obtained when it is in the above range becomes good.
  • a colorant (G) When the negative photosensitive resin composition of the present invention is used for forming a black matrix, which is a grid-like black portion surrounding the three color pixels R, G, and B of a color filter of a liquid crystal display element, a colorant (G ) Is preferably included.
  • the colorant (G) include carbon black, aniline black, anthraquinone black pigment, and perylene black pigment. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned.
  • the colorant (G) a mixture of organic pigments such as red pigments, blue pigments, green pigments, and inorganic pigments can also be used.
  • the negative photosensitive resin composition of the present invention contains a colorant (G) and is used for forming a black matrix or the like
  • the content of the colorant (G) in the total solid content in the negative photosensitive resin composition is 15 to 65% by mass is preferable, and 20 to 50% by mass is particularly preferable.
  • the negative photosensitive resin composition obtained when it is in the above range has good sensitivity, and the formed partition has excellent light shielding properties.
  • the negative photosensitive resin composition of the present invention contains a dispersible material such as the colorant (G), it preferably contains a polymer dispersant (H) in order to improve the dispersibility.
  • the polymer dispersant (H) is not particularly limited, but is urethane, polyimide, alkyd, epoxy, polyester, melamine, phenol, acrylic, polyether, vinyl chloride, vinyl chloride acetic acid.
  • a vinyl copolymer system, a polyamide system, a polycarbonate system, and the like can be mentioned, and a urethane system or a polyester system is preferable.
  • the polymer dispersant (H) may have a structural unit derived from ethylene oxide and / or propylene oxide.
  • the polymer dispersant (H) having a basic group should be used in consideration of the affinity for the colorant (G). Is preferred. Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
  • a commercially available product may be used as the polymer dispersant (H). Commercially available products include Disparon DA-7301 (trade name, manufactured by Enomoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all trade names, manufactured by BYK-Chemie), Solspurs 5000, Solspers 17000 (all trade names, Zeneca).
  • the amount of the polymer dispersant (H) used is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, based on the colorant (G). When the amount used is not less than the lower limit of the above range, the dispersibility of the colorant (G) is improved.
  • the negative photosensitive resin composition of the present invention may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as the dispersion aid (I).
  • the dispersion aid (I) is considered to have a function of improving the dispersion stability by adsorbing to the dispersible material such as the colorant (G) and the polymer dispersant (H).
  • the amount of the dispersion aid (I) used is preferably 1 to 10% by mass, particularly preferably 2 to 8% by mass, based on the colorant (G).
  • the amount used is not less than the lower limit of the above range, the dispersion stability of the colorant (G) is improved, and when it is not more than the upper limit of the above range, the developability of the negative photosensitive resin composition becomes good. .
  • silane coupling agent (J) When the negative photosensitive resin composition of the present invention uses a silane coupling agent (J), the substrate adhesion of the formed cured film is improved.
  • the silane coupling agent (J) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyl.
  • trimethoxysilane 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like. These may be used alone or in combination of two or more.
  • the content of the silane coupling agent (J) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass.
  • the content of the silane coupling agent (J) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass.
  • the negative photosensitive resin composition of the present invention may contain fine particles (K) as necessary. By mix
  • the fine particles (K) are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO); organic materials such as polyethylene and polymethyl methacrylate (PMMA)
  • inorganic fine particles are preferable, and in view of availability and dispersion stability, silica or zirconia is particularly preferable.
  • the fine particles (K ) Is preferably negatively charged.
  • the fine particles (K) do not absorb the light irradiated at the time of exposure, i-line (365 nm) which is the main emission wavelength of the ultrahigh 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 (K) is preferably 1 ⁇ m or less, particularly preferably 200 nm or less, since the surface smoothness of the partition wall is improved.
  • the content of the fine particles (K) in the total solid content in the negative photosensitive resin composition is preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass. When the content ratio is not less than the lower limit of the above range, there is an effect of suppressing the decrease in ink repellency due to post-baking, and when it is not more than the upper limit of the above range, the storage stability of the negative photosensitive resin composition is good. Become.
  • the negative photosensitive resin composition of the present invention may contain a phosphoric acid compound (L) as necessary. Adhesiveness with a board
  • substrate can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (L).
  • the phosphoric acid compound (L) include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
  • the content ratio of the phosphoric acid compound (L) 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 of the present invention may further contain a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, and the like as necessary. .
  • a photopolymerization initiator comprising at least one selected from 1-one and 4,4′-bis (diethylamino) benzophenone, and having a total solid content of 0.1 to 50 in a negative photosensitive resin composition mass%
  • An ink agent 0.01 to 10% by mass in the total solid content of the negative photosensitive resin composition
  • Solvent (D) The total amount of the solvent (D) is diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 3-methoxybutyl acetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, 4- A solvent (D) containing 50 to 90% by mass of a solvent (D1) selected from butyrolactone and cyclohexanol acetate and 10 to 50% by mass of a solvent (D2) selected from water, 2-propanol and propylene glycol monomethyl ether, respectively. In a negative photosensitive resin composition in an amount of 50 to 99% by mass.
  • the alkali-soluble resin (A), the photopolymerization initiator (B), and the ink repellent agent (C) are the same as in the combination 1-1, and the solvent (D) is as follows.
  • a photopolymerization initiator comprising at least one selected from 1-one and 4,4′-bis (diethylamino) benzophenone, and having a total solid content of 0.1 to 50 in a negative photosensitive resin composition mass%
  • An ink agent 0.01 to 10% by mass in the total solid content of the negative photosensitive resin composition
  • Solvent (D) The total amount of the solvent (D) is diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 3-methoxybutyl acetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, 4- 50 to 90% by mass of a solvent (D1) selected from butyrolactone and cyclohexanol acetate, 5 to 45% by mass of a solvent (D2) selected from water, 2-propanol and propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2 -5 to 45% by mass of a solvent (D3) selected from acetate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate and solvent naphtha Each contains 50 to 99% by weight solvent (D) to the negative photosensitive resin composition.
  • a solvent (D1) selected from buty
  • Alkali-soluble resin epoxy resin having a biphenyl skeleton represented by the above formula (A1-2a), epoxy resin represented by the above formula (A1-2b), represented by the above formula (A1-2c)
  • An ink agent 0.01 to 10% by mass in the total solid content of the negative photosensitive resin composition
  • Solvent (D) The total amount of the solvent (D) is diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 3-methoxybutyl acetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, 4- 50 to 90% by mass of a solvent (D1) selected from butyrolactone and cyclohexanol acetate, 5 to 45% by mass of a solvent (D2) selected from water, 2-propanol and propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2 -5 to 45% by mass of a solvent (D3) selected from acetate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate and solvent naphtha Each contains 50 to 99% by weight solvent (D) to the negative photosensitive resin composition.
  • a solvent (D1) selected from buty
  • an alkali-soluble resin A
  • a photopolymerization initiator B
  • an ink repellent agent C
  • a solvent D
  • a crosslinking agent E
  • heat Crosslinking agent F
  • colorant G
  • polymer dispersant H
  • dispersion aid I
  • silane coupling agent J
  • fine particles K
  • phosphate compound L
  • other additions A method of mixing with an agent is preferred.
  • 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 is an ordinary negative photosensitive resin composition. It can be used as a member of an optical element in which a cured film is used.
  • the negative photosensitive resin composition of the present invention is used for forming a partition for an optical element having a plurality of pixels and a partition located between adjacent pixels on a substrate, such as ultraviolet / ozone cleaning treatment A partition wall having sufficient ink repellency can be obtained even after the lyophilic treatment, which is preferable.
  • the negative photosensitive resin composition of the present invention in the production of the partition wall, in the film formed using this and dried, the film thickness is uniform and there is no unevenness, and aggregates are formed on the film surface. Good coatability that does not occur.
  • the partition of this invention is a partition formed in order to provide a division on a board
  • the partition of the present invention is suitably used for an optical element.
  • the negative photosensitive resin composition contains a colorant (G)
  • the resulting partition can be applied as a black matrix.
  • the partition of the present invention is applied to a partition for an optical element having, for example, a plurality of pixels and a partition located between adjacent pixels on a substrate.
  • Examples of the method for producing the partition 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 on the substrate to form a coating film (coating film forming process), and then the coating film is dried to form a film (drying process). Only the part to be the partition wall is exposed and photocured (exposure process), and then the coating film other than the photocured part is removed to form the partition wall comprising the photocured part of the coating film (development process) Then, the partition walls for the optical element of the present invention can be manufactured 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
  • FIG. 1 is a cross-sectional view schematically showing a production example of an optical element partition using the negative photosensitive resin composition of the present invention.
  • FIG. 1 (I) is a view showing a cross section in a state where a coating film 2 made of the negative photosensitive resin composition of the present invention is formed on a substrate 1.
  • (II) is a figure which shows an exposure process typically.
  • (III) is sectional drawing which shows the board
  • the manufacturing method of the partition for optical elements using the negative photosensitive resin composition of this invention is demonstrated concretely using FIG.
  • the negative photosensitive resin composition of the present invention is applied onto a substrate 1 to form a coating film 2 made of the negative photosensitive resin composition.
  • substrate 1 is wash
  • the coating method of the negative photosensitive resin composition is not particularly limited as long as a coating film having a uniform film thickness is formed. Spin coating, spraying, slit coating, roll coating, spin coating The method used for normal coating-film formation, such as a method and a bar coating method, is mentioned. In particular, a slit coating method that can be applied to a large area at once is preferable.
  • the negative photosensitive resin composition of the present invention is a surface of the ink repellent agent (C) in the coating of the negative photosensitive resin composition on the substrate and the drying step such as the following prebaking step.
  • the film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained.
  • the film thickness of the coating film 2 is preferably 100 to 200%, particularly preferably 100 to 130% of the height of the partition wall finally obtained.
  • the thickness of the coating film 2 is preferably from 0.3 to 325 ⁇ m, particularly preferably from 1.3 to 65 ⁇ m.
  • the coating film 2 formed on the substrate 1 in the coating film forming step is heated to obtain the film 2.
  • 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.
  • the ink repellent agent (A) moves to the vicinity of the coating film surface.
  • the heating method include a method in which the coating film 2 together with the substrate 1 is heat-treated at 50 to 120 ° C. for about 10 to 2,000 seconds using a heating device such as a hot plate or an oven.
  • a drying step such as vacuum drying other than heating (drying) is performed in order to remove volatile components such as a solvent.
  • drying it is more preferable to use heating and vacuum drying in combination with the drying by the pre-baking process.
  • the conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, but can be preferably performed at 500 to 10 Pa for a wide range of about 10 to 300 seconds.
  • the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern. Only the predetermined pattern portion cut by the mask 4 is transmitted by the light 5, reaches the film on the substrate 1, and only the portion is photocured. Therefore, when the partition is formed, the predetermined pattern is provided in a shape that matches the shape of the partition.
  • the average partition wall width after the post-baking step is preferably 100 ⁇ m or less, and particularly preferably 20 ⁇ m or less. Further, the average distance between adjacent partition walls is preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less. It is preferable to use a mask in which a pattern is formed so as to be in this range.
  • the exposed portion 3 of the film irradiated with light is composed of a cured film of a negative photosensitive resin composition, while the unexposed portion is a film 2 of an uncured negative photosensitive resin composition. It is a state in which it remains.
  • the irradiation light 5 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; Examples include lines. Further, the irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, more preferably a light ray having a distribution in the range of 300 to 500 nm, particularly i-line (365 nm), h-line (405 nm) and g-line (436 nm). preferable.
  • Exposure is preferably 5 ⁇ 1,000mJ / cm 2, particularly preferably 50 ⁇ 400mJ / cm 2.
  • the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition serving as a partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate 1.
  • a high resolution is obtained when it is not more than the upper limit of the above range.
  • the exposure time depends on the exposure amount, the composition of the photosensitive composition, the thickness of the coating film, etc., but is preferably 1 to 60 seconds, and particularly preferably 5 to 20 seconds.
  • an alkaline aqueous 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.
  • Develop time (time for contacting with developer) is preferably 5 to 180 seconds.
  • Examples of the developing method include a liquid piling method, a dipping method, and a shower method.
  • water on the substrate 1 and the partition walls 6 can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen.
  • the partition 6 on the substrate 1 is heated.
  • the heating method include a method in which the partition wall 6 is heat-treated at 150 to 250 ° C. for 5 to 90 minutes with a heating device such as a hot plate or an oven together with the substrate 1.
  • a heating device such as a hot plate or an oven together with the substrate 1.
  • the heating temperature is particularly preferably 180 ° C. or higher.
  • the heating temperature is too low, curing of the partition wall 6 is insufficient, so that sufficient chemical resistance cannot be obtained, and when the ink is injected into the dots 7 in the subsequent inkjet coating process, the solvent contained in the ink As a result, the partition wall 6 may swell or the ink may ooze. On the other hand, if the heating temperature is too high, thermal decomposition of the partition walls 6 may occur.
  • the average partition wall width is preferably 100 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the average distance between adjacent partition walls (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.
  • the partition wall is formed on the substrate by the manufacturing method, for example, the substrate surface exposed in the region surrounded by the substrate and the partition wall is subjected to an ink affinity treatment (ink affinity treatment process), and then the region.
  • An optical element is obtained by injecting ink into the ink jet method to form the pixel (ink injection step).
  • Examples of the lyophilic process include a cleaning process using an alkaline aqueous solution, an ultraviolet cleaning process, an ultraviolet / ozone cleaning process, an excimer cleaning process, a corona discharge process, and an oxygen plasma process.
  • the cleaning process with an alkaline aqueous solution is a wet process in which the substrate surface is cleaned with an alkaline aqueous solution (potassium hydroxide, tetramethyl ammonium hydroxide aqueous solution, or the like).
  • the ultraviolet cleaning process is a dry process for cleaning the substrate surface using ultraviolet rays.
  • the ultraviolet / ozone cleaning process is a dry process that cleans the substrate surface using a low-pressure mercury lamp that emits light of 185 nm and 254 nm.
  • the excimer cleaning process is a dry process for cleaning the substrate surface using a xenon excimer lamp that emits light at 172 nm.
  • the corona discharge treatment is a dry treatment that uses a high-frequency high voltage to generate corona discharge in the air and cleans the substrate surface.
  • the oxygen plasma treatment is a dry treatment in which oxygen is excited in a vacuum mainly using a high frequency power source as a trigger to clean the substrate surface using a highly reactive “plasma state”.
  • a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable because it is simple.
  • UV / ozone can be generated using commercially available equipment.
  • An ink-repellent treatment can be performed by placing a substrate on which a partition wall is formed in an ultraviolet / ozone apparatus and performing the treatment in air at room temperature for about 1 to 10 minutes within a range that does not impair the oil repellency of the partition wall. it can.
  • about processing time what is necessary is just to adjust to the time used as the range which does not impair the oil repellency of a partition according to each ultraviolet-ray / ozone apparatus.
  • the removal of impurities remaining on the dots after the formation of the partition walls can be sufficiently performed to sufficiently measure the dot ink fondness, such as a color display device using an optical element obtained. It is possible to prevent white spots.
  • the partition obtained from the negative photosensitive resin composition of the present invention it is possible to make the ink affinity by the ultraviolet cleaning treatment or the like without reducing the ink repellency of the partition.
  • the ink repellency (water / oil repellency) of the cured film formed from the negative photosensitive resin composition is water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent often used as a solvent for the ink. )
  • the contact angle can be estimated.
  • the water contact angle of the partition walls is preferably 90 ° or more, and particularly preferably 95 ° or more.
  • the contact angle of PGMEA of the partition wall is preferably 30 degrees or more, particularly preferably 35 degrees or more.
  • the dots are required to be ink-philic, and the water
  • the contact angle is preferably 20 degrees or less, and particularly preferably 10 degrees or less.
  • This step can be performed in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method.
  • An ink jet apparatus used for forming such a pixel is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and ink is ejected intermittently using a piezoelectric element.
  • An ink jet apparatus using various methods such as a method, a method of heating ink, and intermittently ejecting the ink using the foaming can be used.
  • optical elements produced using the negative photosensitive resin composition of the present invention include color filters, organic EL elements, and organic TFT arrays.
  • the shape of the pixel to be formed can 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 forming the pixel 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 a water-soluble organic solvent as necessary, a water-soluble resin or a water-dispersible resin as a binder resin component, and 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. Moreover, after injecting an ink by the inkjet method, it is preferable to perform drying, heat curing, and ultraviolet curing as necessary.
  • 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 eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer.
  • a transparent electrode such as tin-doped indium 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 after the dot is made into an ink-inking treatment, a solution of a hole transport material and a light emitting material is sequentially applied to the dot using an ink jet method and dried Thus, a hole 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.
  • An organic TFT array can be manufactured through the following steps (1) to (3).
  • a partition wall is formed on a transparent substrate such as glass using the negative photosensitive resin composition of the present invention.
  • a gate electrode material is formed by applying a solution of a gate electrode material to the dots using an inkjet method.
  • a gate insulating film is formed thereon.
  • a barrier rib is formed on the gate insulating film using the negative photosensitive resin composition of the present invention, and after the dot is made to be an ink-philic treatment, a solution of a source / drain electrode material is applied to the dot using an ink jet method.
  • a drain electrode is formed.
  • a partition is formed using the negative photosensitive resin composition of the present invention so as to surround a region including the pair of source / drain electrodes, and the ink is made to be an ink-insensitive dot. Thereafter, an organic semiconductor solution is applied to the dots using an ink jet method to form an organic semiconductor layer between the source and drain electrodes.
  • the partition using the negative photosensitive resin composition of the present invention may be used in only one step, or the negative photosensitive resin of the present invention in two or more steps. You may utilize the partition using a conductive resin composition.
  • Examples 1 to 5 and 8 to 10 are examples, and examples 6, 7, and 11 are comparative examples.
  • ZAR2002 Trade name; KAYARAD ZAR-2002H, manufactured by Nippon Kayaku Co., Ltd., a resin in which a carboxy group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, an acid value of 60 mgKOH / g, a solid content of 70% by mass, PGMEA: 30% by mass).
  • IR907 Trade name: IRGACURE 907, manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone.
  • EAB 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • OXE02 Trade name; IRGACURE OXE02, manufactured by BASF, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime.
  • Solvent (D) (I) Solvent (D1) EDM: Diethylene glycol ethyl methyl ether. Metoace: 3-methoxybutyl acetate. EEP: ethyl 3-ethoxypropionate. (ii) Solvent (D2) PGME: Propylene glycol monomethyl ether. (iii) Solvent (D3) MDM: Diethylene glycol dimethyl ether. PGMEA: Propylene glycol monomethyl ether acetate. EDGAC: Diethylene glycol monoethyl ether acetate. Solvent naphtha: A mixed solvent of petroleum compounds. Although it has a boiling point in the range of 150 to 200 ° C.
  • the fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the obtained (C2-1) liquid is 18.8 mass%.
  • the number average molecular weight (Mn) of the composition excluding the solvent of the solution (C2-1) was 866.
  • a PGME solution containing 10% by mass of the ink repellent agent (C3) is referred to as (C3-1) solution.
  • the obtained fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the (C3-1) solution is 18.8 mass%.
  • the number average molecular weight (Mn) of the composition excluding the solvent of the solution (C3-1) was 768.
  • Example 1 (Preparation of negative photosensitive resin composition) (C1-1) solution 10 g (solid content is 1.0 g, the rest is PGME of the solvent), CCR-1235 75 g (solid content is 45 g, the rest is the solvent EDGAC: 20 g, solvent naphtha: 10 g), IR907 6 g, 3 g of EAB, 45 g of A9530, 180 g of EDM, and 81 g of PGME were placed in a stirring vessel of 1,000 cm 3 and stirred for 30 minutes to prepare negative photosensitive resin composition 1.
  • Table 1 shows the composition in the solid content of the negative photosensitive resin composition, the composition in the solvent component, and the content of the solvent (D) component in the composition.
  • the negative photosensitive resin composition 1 was applied to the cleaned glass substrate surface using a spinner and then dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1.3 ⁇ m.
  • a gap of 50 ⁇ m is formed on the surface of the obtained film from the film side through a photomask having a hole pattern (2.5 cm ⁇ 5 cm) (a photomask in which light is irradiated to a region other than the pattern portion). Then, ultraviolet rays from a high-pressure mercury lamp were irradiated at 25 mW / cm 2 for 10 seconds to obtain a cured film.
  • the exposed glass substrate was developed by immersing in a 0.4% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the unexposed film was washed away with water and dried. Next, this was heated on a hot plate at 230 ° C. for 20 minutes to obtain a glass substrate (1) in which a cured film of the negative photosensitive resin composition 1 was formed in a region excluding the hole pattern portion. .
  • In-plane uniformity (maximum film thickness-minimum film thickness) / (2 ⁇ average film thickness) ⁇ 100
  • the results were evaluated as follows.
  • the film thickness of Table 1 is an average value of the film thickness measured at this time. The evaluation results are shown in Table 1. ⁇ (Good): 5% or less. X (defect): It exceeds 5%.
  • ⁇ Appearance of cured film > The appearance of the cured film in the chromium metal vapor deposition substrate (3) produced in Production 3 of the cured film was visually observed under a sodium lamp, and unevenness was evaluated as follows. ⁇ (Good): Circular unevenness and unevenness such as chuck marks are not visible. X (defect): Circular irregularities and irregularities such as chuck marks are visible.
  • ⁇ Storage stability> The negative photosensitive composition was stored in a glass screw bottle at 23 ° C. (room temperature) for 2 weeks. After storage for 2 weeks, the negative photosensitive composition was applied to the surface of a 10 cm ⁇ 10 cm glass substrate washed by the same method as in Production of cured film 1 using a spinner to form a coating film. Furthermore, it was dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1 ⁇ m. The appearance of the film was visually observed and evaluated as follows. (Excellent): There are 5 or less foreign matters on the film. ⁇ (Good): There are 6 to 20 foreign substances on the film. X (defect): There were 21 or more foreign substances on the film, and radial streaks were observed from the center of the glass substrate.
  • Example 2 to 11 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and the negative photosensitive resin composition film and cured film were formed as a glass substrate (1), glass A substrate (2) and a chromium metal vapor deposition film substrate (3) were obtained. These were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the negative photosensitive resin composition had good appearance with no unevenness or aggregates in the film. Furthermore, the in-plane uniformity was also good. Further, the cured film obtained from the negative photosensitive resin composition exhibits good ink repellency, maintains high ink repellency even after irradiation with ultraviolet rays / ozone, and the glass substrate surface has good hydrophilicity. I understand that.
  • Example 6 Although sufficient ink repellency was obtained, but unevenness in appearance and aggregates were generated, and in-plane uniformity was low.
  • Example 11 although sufficient ink repellency was obtained, the appearance was uneven and the in-plane uniformity was low.
  • the negative photosensitive resin composition of the present invention is a negative photosensitive resin composition capable of producing a partition having good ink repellency and capable of retaining ink repellency even when irradiated with ultraviolet rays / ozone.
  • a film obtained by using this to form a coating film and dried has a uniform film thickness, no unevenness, and good coating properties in which no aggregate is generated on the film surface. Therefore, the obtained partition walls also have good appearance and uniform film thickness.
  • the partition walls are formed for color filter manufacturing, organic EL element manufacturing, and organic TFT array manufacturing using the inkjet recording technology method. In particular, it is preferably used for forming a partition wall of a large-area substrate.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
PCT/JP2012/071613 2011-08-30 2012-08-27 ネガ型感光性樹脂組成物、隔壁および光学素子 WO2013031737A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2013531309A JP6136928B2 (ja) 2011-08-30 2012-08-27 ネガ型感光性樹脂組成物、隔壁の製造方法および光学素子の製造方法
CN201280042624.9A CN103765314B (zh) 2011-08-30 2012-08-27 负型感光性树脂组合物、分隔壁以及光学元件
KR1020147005137A KR101923249B1 (ko) 2011-08-30 2012-08-27 네거티브형 감광성 수지 조성물, 격벽 및 광학 소자

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011187764 2011-08-30
JP2011-187764 2011-08-30

Publications (1)

Publication Number Publication Date
WO2013031737A1 true WO2013031737A1 (ja) 2013-03-07

Family

ID=47756225

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/071613 WO2013031737A1 (ja) 2011-08-30 2012-08-27 ネガ型感光性樹脂組成物、隔壁および光学素子

Country Status (5)

Country Link
JP (1) JP6136928B2 (zh)
KR (1) KR101923249B1 (zh)
CN (1) CN103765314B (zh)
TW (1) TWI529492B (zh)
WO (1) WO2013031737A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014197153A (ja) * 2013-03-29 2014-10-16 三洋化成工業株式会社 感光性樹脂組成物
CN105829100A (zh) * 2013-12-17 2016-08-03 旭硝子株式会社 负型感光性树脂组合物、树脂固化膜、分隔壁和光学元件

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106465508B (zh) * 2014-06-09 2018-05-25 旭硝子株式会社 拒墨剂、负型感光性树脂组合物、分隔壁和光学元件
KR102541614B1 (ko) * 2015-03-04 2023-06-09 다이요 홀딩스 가부시키가이샤 에칭 레지스트 조성물 및 드라이 필름
JP6697222B2 (ja) * 2015-03-04 2020-05-20 太陽インキ製造株式会社 エッチングレジスト組成物およびドライフィルム
SG11201807874YA (en) * 2016-03-28 2018-10-30 Toray Industries Photosensitive resin composition
KR102395742B1 (ko) * 2017-03-31 2022-05-09 동우 화인켐 주식회사 청색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 화상 표시 장치
TWI662069B (zh) * 2018-07-11 2019-06-11 新應材股份有限公司 感光性組成物、彩色濾光片及彩色濾光片的製造方法
WO2020075592A1 (ja) * 2018-10-12 2020-04-16 東レ株式会社 感光性樹脂組成物、硬化膜、および該硬化膜を用いた表示装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010128129A (ja) * 2008-11-27 2010-06-10 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物
JP2010170093A (ja) * 2008-11-12 2010-08-05 Sumitomo Chemical Co Ltd 感光性黒色樹脂組成物、ブラックマトリクス基板およびカラーフィルタの製造方法
JP2011048195A (ja) * 2009-08-27 2011-03-10 Asahi Glass Co Ltd 光学素子隔壁形成用感光性組成物、これを用いたブラックマトリックスおよびその製造方法、並びにカラーフィルタオンアレイの製造方法
JP2011089108A (ja) * 2009-09-28 2011-05-06 Fujifilm Corp 分散組成物及びその製造方法、遮光性カラーフィルタ用感光性樹脂組成物及びその製造方法、遮光性カラーフィルタ及びその製造方法、並びに固体撮像素子
JP2011165396A (ja) * 2010-02-05 2011-08-25 Mitsubishi Chemicals Corp アクティブ駆動型有機電界発光素子の隔壁用感光性組成物およびアクティブ駆動型有機電界発光表示装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4671338B2 (ja) * 2005-06-27 2011-04-13 日本化薬株式会社 フッ素含有ポリシロキサン、それを用いる感光性樹脂組成物及びその硬化物
JP5162861B2 (ja) * 2005-09-29 2013-03-13 Ｊｎｃ株式会社 フッ素を含有した光硬化性重合体組成物
TW200722795A (en) * 2005-11-02 2007-06-16 Fujifilm Corp Substrate with dividing walls for an inkjet color filter, method for manufacturing the substrate, color filter including the substrate with dividing walls for an inkjet color filter and method of menufacturing the color filter, and liquid crystal display
WO2007069593A1 (ja) * 2005-12-16 2007-06-21 Fujifilm Corporation カラーフィルタ用隔壁の製造方法、カラーフィルタ用隔壁付基板、表示素子用カラーフィルタ、及び表示装置
KR101269299B1 (ko) * 2008-08-01 2013-05-29 아사히 가라스 가부시키가이샤 네거티브형 감광성 조성물, 그것을 사용한 광학 소자용 격벽 및 그 격벽을 갖는 광학 소자
JP2011065396A (ja) 2009-09-17 2011-03-31 Namco Bandai Games Inc プログラム、情報記憶媒体及びオブジェクト生成システム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010170093A (ja) * 2008-11-12 2010-08-05 Sumitomo Chemical Co Ltd 感光性黒色樹脂組成物、ブラックマトリクス基板およびカラーフィルタの製造方法
JP2010128129A (ja) * 2008-11-27 2010-06-10 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物
JP2011048195A (ja) * 2009-08-27 2011-03-10 Asahi Glass Co Ltd 光学素子隔壁形成用感光性組成物、これを用いたブラックマトリックスおよびその製造方法、並びにカラーフィルタオンアレイの製造方法
JP2011089108A (ja) * 2009-09-28 2011-05-06 Fujifilm Corp 分散組成物及びその製造方法、遮光性カラーフィルタ用感光性樹脂組成物及びその製造方法、遮光性カラーフィルタ及びその製造方法、並びに固体撮像素子
JP2011165396A (ja) * 2010-02-05 2011-08-25 Mitsubishi Chemicals Corp アクティブ駆動型有機電界発光素子の隔壁用感光性組成物およびアクティブ駆動型有機電界発光表示装置

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014197153A (ja) * 2013-03-29 2014-10-16 三洋化成工業株式会社 感光性樹脂組成物
CN105829100A (zh) * 2013-12-17 2016-08-03 旭硝子株式会社 负型感光性树脂组合物、树脂固化膜、分隔壁和光学元件
JPWO2015093415A1 (ja) * 2013-12-17 2017-03-16 旭硝子株式会社 ネガ型感光性樹脂組成物、樹脂硬化膜、隔壁および光学素子
US10067421B2 (en) 2013-12-17 2018-09-04 Asahi Glass Company, Limited Negative photosensitive resin composition, cured resin film, partition walls and optical element

Also Published As

Publication number Publication date
TWI529492B (zh) 2016-04-11
KR20140061429A (ko) 2014-05-21
TW201319752A (zh) 2013-05-16
CN103765314B (zh) 2018-02-16
JP6136928B2 (ja) 2017-05-31
CN103765314A (zh) 2014-04-30
KR101923249B1 (ko) 2018-11-28
JPWO2013031737A1 (ja) 2015-03-23

Similar Documents

Publication Publication Date Title
JP5093352B2 (ja) ネガ型感光性組成物、それを用いた光学素子用隔壁および該隔壁を有する光学素子
JP5910629B2 (ja) ネガ型感光性樹脂組成物、硬化膜、隔壁およびブラックマトリックスとその製造方法、カラーフィルタならびに有機ｅｌ素子
JP6136928B2 (ja) ネガ型感光性樹脂組成物、隔壁の製造方法および光学素子の製造方法
JP6115471B2 (ja) ネガ型感光性樹脂組成物、隔壁、ブラックマトリックス及び光学素子
JP5803938B2 (ja) ネガ型感光性樹脂組成物、光学素子用隔壁およびその製造方法、ならびに、該隔壁を有する光学素子の製造方法
JP6036699B2 (ja) 撥インク剤の製造方法、ネガ型感光性樹脂組成物、隔壁および光学素子
WO2013031736A1 (ja) 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
JP6593331B2 (ja) 撥インク剤、ネガ型感光性樹脂組成物、隔壁および光学素子
JP2013050549A (ja) ネガ型感光性樹脂組成物、隔壁、光学素子
JP6020557B2 (ja) ネガ型感光性樹脂組成物、硬化膜、隔壁および光学素子
WO2015093415A1 (ja) ネガ型感光性樹脂組成物、樹脂硬化膜、隔壁および光学素子
JP2008298859A (ja) 感光性組成物、それを用いた隔壁、隔壁の製造方法、カラーフィルタの製造方法、有機ｅｌ表示素子の製造方法および有機ｔｆｔアレイの製造方法
WO2012132755A1 (ja) ネガ型感光性樹脂組成物および塗膜
WO2014046209A1 (ja) 撥インク性組成物、ネガ型感光性樹脂組成物、硬化膜、隔壁、及び光学素子
WO2014046210A1 (ja) 部分加水分解縮合物およびこれを用いた撥インク剤
WO2018116914A1 (ja) ネガ型感光性樹脂組成物
WO2012176816A1 (ja) ネガ型感光性樹脂組成物、隔壁、ブラックマトリックス、カラーフィルタおよび液晶表示素子
JP2019164341A (ja) ネガ型感光性樹脂組成物、それを用いたフォトスペーサーおよび画像表示装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12827615

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013531309

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20147005137

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12827615

Country of ref document: EP

Kind code of ref document: A1