WO2011081151A1 - Composition photosensible, paroi de séparation, filtre coloré et élément électroluminescent organique - Google Patents

Composition photosensible, paroi de séparation, filtre coloré et élément électroluminescent organique Download PDF

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Publication number
WO2011081151A1
WO2011081151A1 PCT/JP2010/073603 JP2010073603W WO2011081151A1 WO 2011081151 A1 WO2011081151 A1 WO 2011081151A1 JP 2010073603 W JP2010073603 W JP 2010073603W WO 2011081151 A1 WO2011081151 A1 WO 2011081151A1
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WIPO (PCT)
Prior art keywords
group
polymer
photosensitive composition
partition
side chain
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PCT/JP2010/073603
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English (en)
Japanese (ja)
Inventor
秀幸 高橋
健二 石関
正行 川島
光太郎 山田
Original Assignee
旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to KR1020127015702A priority Critical patent/KR101810702B1/ko
Priority to JP2011547696A priority patent/JP5682573B2/ja
Priority to CN201080057676.4A priority patent/CN102656517B/zh
Publication of WO2011081151A1 publication Critical patent/WO2011081151A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—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
    • G03F7/027—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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • 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

Definitions

  • the present invention relates to a photosensitive composition, a partition using the same, a color filter having the partition, and an organic EL device.
  • partition walls between pixels of a color filter partition walls between pixels of an organic EL (Electro-Luminescence) display element, partition walls partitioning each TFT of an organic TFT (Thin Film Transistor) array, partition walls of an ITO electrode of a liquid crystal display element
  • a photosensitive composition has attracted attention.
  • a barrier rib pattern (which may also serve as a black matrix) is formed using photolithography, and then R (red), G (green), and B (blue) ink is applied to the openings between the partition walls to form pixels.
  • an organic EL element after forming a partition pattern using photolithography, a solution such as a hole transport material and a light emitting material is applied to the opening between the partitions using an inkjet method, A pixel having a hole transport layer, a light emitting layer, and the like is formed.
  • the upper surface of the partition wall needs to have a property of repelling ink, so-called liquid repellency.
  • the opening between the partition walls needs to have a property of getting wet with ink, so-called lyophilic property.
  • Patent Document 1 describes a photosensitive resin composition containing a repeating unit having at least a fluorine atom in a side chain and a repeating unit having a polyether structure in a side chain.
  • the mass average molecular weight of the fluorine-containing compound described in the examples of Patent Document 1 is 26,000 at the maximum.
  • Patent Document 2 discloses a photopolymerizable compound, an ink repellent compound that is a copolymer obtained by copolymerizing at least a fluorine-containing monomer and a monomer containing an alkylene group having an etheric oxygen atom, a photopolymerization initiator, The coloring photosensitive resin composition containing a coloring agent is described.
  • the maximum weight average molecular weight of the fluorine-containing copolymer described in the examples of Patent Document 2 is 10,900.
  • the required performance of the obtained partition wall that is, good ink repellency at the top of the partition wall, and erosion to the developer Performance such as resistance to the developer not developed, good wetting and spreading of the ink to the opening between the partition walls, etc. are sufficiently obtained, but when using a fluorine-containing resin having no ethylenic double bond, these performances
  • the present condition is that the partition which fully satisfy
  • the present invention was made in order to solve the problems of the prior art, and although it is an ink repellent component that does not have an ethylenic double bond, it has good ink repellency at the upper part of the partition wall and is not eroded by the developer. Contains an ink repellent component that can impart to the resulting partition the resistance to developer, the property of suppressing the generation of residual film that remains without being developed, and the good ink wetting and spreading property to the opening between the partitions.
  • the present invention provides a photosensitive composition, partition walls, a color filter, and an organic EL device having the following configuration.
  • a polymer (A) having a side chain having a group represented by the following general formula (1) and a side chain having a polyoxyalkylene group and having no side chain having an ethylenic double bond;
  • a photosensitive composition comprising a photocuring initiator (B) and a binder resin (C), -CFXR f (1)
  • X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group
  • R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom.
  • the polymer (A) has a mass average molecular weight (Mw (A)) of 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4 .
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group which may be substituted with a fluorine atom;
  • R 3 is a hydrogen atom or a carbon number; Represents an organic group of 1 to 10 and n represents an integer of 1 to 200.
  • a side chain having a group represented by the general formula (2) and a side chain having a polyoxyalkylene group, and having a group represented by the general formula (1) and an ethylenic group It is a polymer (A) ′ having no side chain having a double bond, and its mass average molecular weight (Mw (A) ′) is 2.6 ⁇ 10 4 ⁇ Mw (A) ′ ⁇ 20 ⁇ 10. 4.
  • the photosensitive composition according to any one of [1] to [7], further comprising a polymer (A) ′ that is 4 .
  • the photocuring initiator (B) is a photopolymerization initiator
  • the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond.
  • the photosensitive composition in any one.
  • a color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is formed by the partition described in [12], and the pixel is formed by an inkjet method A color filter characterized by being made.
  • the term “photocuring initiator” is used as a general term for compounds that generate active species by light irradiation to initiate the curing reaction of the binder resin (C).
  • the polyoxyalkylene group is a divalent group represented by — (RO) p — (R represents an alkylene group, and p represents an integer of 2 or more).
  • RO represents an alkylene group, and p represents an integer of 2 or more.
  • One end of the polyoxyalkylene group is bonded to the terminal group, and the other end is a bond bonded to the main chain side of the polymer.
  • the obtained partition wall has good ink repellency at the top of the partition wall, developer resistance not eroded by the developer, and without development. It is possible to impart the property of suppressing the generation of remaining residual film and the good ink spreading property to the opening between the partition walls.
  • a partition wall that is economically advantageous and has good performance, and a color filter and an organic EL device having the partition wall are obtained.
  • the (meth) acryloyl group is used as a general term meaning both an acryloyl group and a methacryloyl group.
  • (Meth) acrylate is used as a generic term for both acrylate and methacrylate.
  • (Meth) acrylic acid is used as a generic term for both acrylic acid and methacrylic acid.
  • (Meth) acrylamide is used as a general term for both acrylamide and methacrylamide.
  • (Meth) allyl is used as a generic term for both allyl and methallyl.
  • the group represented by the general formula (1) is also referred to as a group (1). The same applies to other groups.
  • Photosensitive composition of the present invention has a side chain having a group represented by the following general formula (1) and a side chain having a polyoxyalkylene group, and an ethylenic double bond.
  • X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group
  • R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom.
  • the photosensitive composition of the present invention is a photosensitive composition comprising the polymer (A), a photocuring initiator (B), and a binder resin (C), and is a binder in a light irradiation portion upon exposure in photolithography or the like. It is a negative photosensitive composition in which the resin (C) is cured by the action of the photocuring initiator (B). In photolithography or the like, a portion that is not irradiated with light (an unexposed portion) is selectively removed during alkali development performed after exposure, and as a result, a partition wall made of a cured product of the photosensitive composition is formed. It is formed.
  • the negative photosensitive composition is classified into several types such as a radical curable type and an acid curable type depending on the type of curing, and depending on the type of curing, the photocuring initiator (B) and the binder resin ( A combination of C) is selected.
  • the photosensitive composition of the present invention can be applied to any curing type as long as it is a negative photosensitive composition, but is particularly suitable for a radical curable photosensitive composition.
  • an embodiment of the photosensitive composition of the present invention will be described using a radical curable photosensitive composition and an acid curable photosensitive composition as examples.
  • the photosensitive composition of the present invention is a radical curable type
  • the photosensitive composition contains a polymer (A) and a photopolymerization initiator (B) as a photocuring initiator (B).
  • Such a radical curable photosensitive composition is a coating film cured product in which the photosensitive resin (C1) is radically polymerized by the action of the photopolymerization initiator (B1) in the light-irradiated portion during exposure in photolithography or the like, and curing is accelerated.
  • Each component which the radical curable photosensitive composition concerning this invention contains is demonstrated below.
  • Polymer (A) has a side chain having the group represented by the general formula (1), has a polyoxyalkylene group, and does not have a side chain having an ethylenic double bond.
  • the mass average molecular weight (Mw (A)) is 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4 .
  • the polymer (A) Since the polymer (A) has a side chain having the fluorine atom-containing group (1) and has a high molecular weight such that the mass average molecular weight is shown in the above range, the photosensitivity of the present invention on the substrate. When the coating film formed by applying the composition is dried, it tends to move to the vicinity of the surface of the coating film.
  • the polymer (A) does not have an ethylenic double bond in the side chain, but has a high molecular weight as in the mass average molecular weight range, so that the photosensitive composition is cured by exposure after drying the coating film. As the film advances, it remains in the vicinity of the surface of the coating film transferred during drying of the coating film and is easily fixed at that position.
  • the solubility of the developer is sufficiently ensured by setting the mass average molecular weight within the above range.
  • the partition formed by developing the coated film after exposure can exhibit liquid repellency on the top surface, and can also exhibit lyophilicity at the opening between the partitions. It becomes.
  • the polymer (A) does not migrate to the openings, and lyophilicity can be maintained in the openings between the partition walls. .
  • the polymer (A) has a side chain having a polyoxyalkylene group, the liquid repellency can be maintained even when a jet rinsing step using high-pressure water after the development step is performed.
  • the reason why the phenomenon is observed is not necessarily clear, but is considered as follows. Due to the interaction between the polyoxyalkylene group and other components such as the binder resin (C), the so-called anchor effect, the polymer (A) is considered to be less likely to be detached from the coating film surface. In particular, when the jet rinsing step using high-pressure water after the development step is performed, the polymer (A) is easily detached from the surface layer.
  • the polymer (A) has a side chain having a polyoxyalkylene group, due to the anchor effect, the polymer (A) tends to remain on the surface of the coating film, and the coating film tends to exhibit liquid repellency. There is. For this reason, when ink is applied to the opening surrounded by the partition wall using the inkjet method, it is possible to suppress the occurrence of color mixing between adjacent openings and the occurrence of white spots in the openings. Moreover, a polymer (A) can suppress generation
  • the phenomenon that the remaining film is generated is considered as follows. Since an alkaline developer used for producing barrier ribs or the like by photolithography or the like generally contains a surfactant, bubbles are easily generated in the development process. Moreover, when this bubble adheres to the liquid-repellent surface, it is difficult to remove. Therefore, there is a tendency that the ink repellent component contained in the photosensitive composition remains in the form of a film due to the bubbles adhering to the portion that should be dissolved and removed by the alkaline developer.
  • the polymer (A) having a side chain having a polyoxyalkylene group can suppress the generation of the remaining film thus generated.
  • the mass average molecular weight (Mw (A)) of the polymer (A) used in the present invention is 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4 . More preferably, 3.0 ⁇ 10 4 ⁇ Mw (A) ⁇ 12 ⁇ 10 4 , still more preferably 3.5 ⁇ 10 4 ⁇ Mw (A) ⁇ 12 ⁇ 10 4 , and particularly preferably, 4.0 ⁇ 10 is a 4 ⁇ Mw (a) ⁇ 10 ⁇ 10 4.
  • the mass average molecular weight of the polymer (A) is 2.6 ⁇ 10 4 or less, the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method. Does not spread out sufficiently.
  • the mass average molecular weight exceeds 20 ⁇ 10 4 , alkali solubility and developability become insufficient.
  • the mass average molecular weight (Mw (A)) is in the range of more than 3.0 ⁇ 10 4 and less than 12 ⁇ 10 4 , the liquid repellency is kept high regardless of the type and concentration of alkali and jet rinse conditions. It is preferable because it is easy to sag and has a wide manufacturing margin. Moreover, it is preferable also from the ease of manufacture of a polymer (A).
  • the number average molecular weight (Mn (A)) of the polymer (A) is preferably 1.0 ⁇ 10 4 ⁇ Mn (A) ⁇ 15.0 ⁇ 10 4 , and 1.5 ⁇ 10 4 ⁇ It is more preferable that Mn (A) ⁇ 12.0 ⁇ 10 4 , and it is particularly preferable that 2.0 ⁇ 10 4 ⁇ Mn (A) ⁇ 10.0 ⁇ 10 4 .
  • the number average molecular weight of the polymer (A) is less than 1.0 ⁇ 10 4 , the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method.
  • a mass average molecular weight (Mw) and a number average molecular weight (Mn) mean the value which measured polystyrene as a standard substance by the gel permeation chromatography method.
  • a photosensitive composition particularly a photosensitive composition containing a black colorant, may not sufficiently proceed with a curing reaction at the time of exposure, but the polymer (A) that is not immobilized at the time of exposure is exposed to light.
  • post-baking which will be described later
  • the film may move to the side surfaces of the partition walls or may flow out to the openings between the partition walls.
  • the mass average molecular weight of the polymer (A) exceeds 2.6 ⁇ 10 4 , and more preferably the number average molecular weight is 1.0 ⁇ 10 4 or more, the migration / outflow of the polymer (A) during the post-baking It is thought that the phenomenon is suppressed.
  • the molecular weight distribution represented by mass average molecular weight (Mw (A)) / number average molecular weight (Mn (A)) is 1.2 or more and 8 or less. Preferably, 1.3 or more and 4 or less are more preferable.
  • Mw (A) mass average molecular weight
  • Mn (A) number average molecular weight
  • the molecular weight distribution in the polymer (A) is within this range, the production process of the polymer (A) can be simplified, which is economically advantageous, and the developability is also good.
  • the polymer (A) used for this invention has group (1) containing the fluorine atom shown by the said General formula (1) in a side chain.
  • R f when R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, R f may have a halogen atom excluding a fluorine atom. Good. As such a halogen atom, a chlorine atom is preferable.
  • the structure of the fluoroalkyl group is not particularly limited, and examples thereof include a linear structure, a branched structure, a ring structure, a structure having a partial ring, and the like, and a linear structure is preferable.
  • R f is a fluoroalkyl group having an etheric oxygen atom
  • the etheric oxygen atom may be present between the carbon-carbon bonds of the fluoroalkyl group or at the end of the fluoroalkyl group. May be.
  • R f in the group (1) is preferably a fluoroalkyl group having 1 to 20 carbon atoms which may have the etheric oxygen atom.
  • X is particularly preferably a fluorine atom.
  • R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom
  • R f is particularly limited as long as it has such a configuration.
  • R f specifically, —CF 3 , —CF 2 CF 3 , —CF 2 CHF 2 , — (CF 2 ) 2 CF 3 , — (CF 2 ) 3 CF 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 5 CF 3 , — (CF 2 ) 6 CF 3 , — (CF 2 ) 7 CF 3 , — (CF 2 ) 8 CF 3 , — (CF 2 ) 9 CF 3 , — ( CF 2 ) 11 CF 3 , — (CF 2 ) 15 CF 3 , —CF (CF 3 ) O (CF 2 ) 5 CF 3 , —CF 2 O (CF 2 CF 2 O) p
  • R f is carbon atoms, which may have an etheric oxygen atom is 1 to 20 fluoroalkyl group, the R f, a perfluoroalkyl group and an etheric oxygen atom having no etheric oxygen atom A perfluoroalkyl group having an etheric oxygen atom is more preferable.
  • the number of carbon atoms is preferably 1 to 11 and particularly preferably 3 to 5.
  • a perfluoroalkyl group or a polyfluoroalkyl group having one hydrogen atom is preferable, and a perfluoroalkyl group is particularly preferable.
  • the perfluoroalkyl group and the polyfluoroalkyl group include those having an etheric oxygen atom.
  • the compound whose X is a hydrogen atom is preferable.
  • the group (1) preferably has 4 to 6 carbon atoms.
  • Specific examples of such a group (1) include — (CF 2 ) 3 CF 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 5 CF 3 , —CF 2 O (CF 2 ) 2 OCF 3 , -CF 2 O (CF 2 ) 2 O (CF 2 ) 2 OCF 3 and the like.
  • the polymer (A) has 4 to 6 carbon atoms in the side chain (1), the compatibility between the polymer (A) and other components constituting the photosensitive composition can be improved. Can do. Thereby, aggregation of a polymer (A) in the coating film formed by apply
  • the number of introduced groups (1) in the side chain having the group (1) is 1.
  • the group (1) may be the same or different. That is, the group (1) that the polymer (A) has in the side chain may be only one type or a combination of two or more types.
  • the group (1) may be introduced into all side chains, but preferably the polymer (A) so as to have the following fluorine atom content. The ratio of the side chain into which the group (1) is introduced relative to the whole is appropriately adjusted. Specifically, when the polymer (A) is produced by polymerizing the raw material monomer as described later, the blending amount of the monomer having the group (1) with respect to the entire raw material monomer is adjusted.
  • the position of introduction of the side chain having the group (1) in the polymer (A) is not particularly limited, and is preferably regular and regularly spaced in a block manner so as to have the following fluorine atom content.
  • the side chain which has group (1) in the principal chain which comprises a polymer (A) can be introduce
  • the side chain having the group (1) is composed of an alternating copolymer, a block copolymer, and a random copolymer. It may be introduced in any form.
  • the polymer (A) is preferably a random copolymer from the viewpoints of production efficiency, intramolecular uniformity of the liquid repellent component, compatibility with components other than the liquid repellent component, and the like.
  • the fluorine atom content in the polymer (A) mainly due to the side chain having the group (1) is preferably 20 to 50% by mass, It is more preferably 25 to 42% by mass, and particularly preferably 25 to 35% by mass. If the fluorine atom content in the polymer (A) is less than 20% by mass, sufficient development resistance tends to be not obtained, and as a result, the liquid repellency of the upper surface of the partition wall may be insufficient. . Further, when the fluorine atom content in the polymer (A) exceeds 50% by mass, the polymers (A) tend to self-aggregate, and as a result, the liquid repellency of the upper surface of the partition wall becomes insufficient. Sometimes. Furthermore, the adhesion between the partition walls and the substrate may be reduced.
  • the fluorine atom content in the polymer (A) is a content mainly derived from the fluorine atom of the group (1) that the polymer (A) has in the side chain.
  • the fluorine atom and the group refers to the content of fluorine atoms combined with the fluorine atoms of the polymer (A).
  • the polymer (A) used in the present invention has a side chain having a polyoxyalkylene group.
  • This polyoxyalkylene group is a polyoxyalkylene group having a repeating unit of an oxyalkylene group having 2 to 4 carbon atoms.
  • the content of the polyoxyalkylene group in the polymer (A) used in the present invention is preferably 5 to 60% by mass. More preferably, it is 10 to 55% by mass, and particularly preferably 15 to 50% by mass.
  • the liquid repellency may be significantly lowered when a jet rinsing process using high-pressure water is performed after the development process. Furthermore, there is a possibility that a large amount of residual film exists in the partition walls and partition opening portions finally obtained.
  • the content of the polyoxyalkylene group exceeds 60% by mass, the liquid repellency may be lowered.
  • the polyoxyalkylene group used in the present invention is specifically a group represented by the following general formula (11) (hereinafter sometimes referred to as group (11)).
  • group (11) -(R 11 O) m (R 12 O) j R 13 (11)
  • R 11 represents an ethylene group
  • R 12 represents an alkylene group having 3 or 4 carbon atoms
  • R 13 represents a hydrogen atom or an optionally substituted substituent having 1 to 10 carbon atoms.
  • m represents an integer of 4 to 100
  • j represents an integer of 0 to 100
  • m + j is 4 to 100.
  • R 11 represents an ethylene group (—CH 2 CH 2 —)
  • R 12 represents an alkylene group having 3 or 4 carbon atoms.
  • the structure of the alkylene group having 3 or 4 carbon atoms may be a linear structure or a branched structure.
  • R 12 is a propylene group (—CH 2 CH (CH 3 ) —), a trimethylene group (—CH 2 CH 2 CH 2 —), an ethylethylene group (—CH 2 CH (CH 2 CH 3 ) —), 1, Examples include 2-dimethylethylene group (—CH (CH 3 ) CH (CH 3 ) —), tetramethylene group (— (CH 2 ) 4 —), and propylene group or tetramethylene group is preferable.
  • m represents an integer of 4 to 100
  • j represents an integer of 0 to 100, respectively, preferably 50 or less, more preferably 30 or less.
  • m / (m + j) which is the ratio of the number of R 11 in the polyoxyalkylene group, is preferably 50 to 100%, more preferably 80 to 100%, and substantially 100%. It is particularly preferred.
  • M + j is 4 to 100, preferably 6 to 50, and more preferably 8 to 30.
  • (R 11 O) m (R 12 O) j is a group (11) having m (R 11 O) units and j (R 12 O) units.
  • the order of bonding between the (R 11 O) unit and the (R 12 O) unit is not particularly limited. That is, in the group (11), m (R 11 O) units and j (R 12 O) units may be bonded alternately, randomly, or in blocks.
  • R 13 when R 13 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, the structure is a straight chain structure, a branched structure, a ring structure, a partial ring It may have a structure or the like.
  • the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms.
  • R 13 in the group (11) is preferably a linear or unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.
  • the polyoxyalkylene group such as the group (11) in the side chain of the polymer (A) one type may be used alone, or two or more types may be used in combination.
  • the introduction of the side chain having the group (11) into the polymer (A) is, as will be described later, when the polymer (A) is produced by polymerizing the raw material monomer.
  • the blending amount of the monomer with respect to the whole raw material monomer is appropriately adjusted so that the blending amount can give the effect of improving the developability to the polymer (A) without impairing the effects of the present invention. .
  • the polymer (A) contained in the photosensitive composition of the present invention is a side having a functional group corresponding to various purposes in addition to the side chain having the group (1) within the range not impairing the effects of the present invention. It is possible to have chains.
  • a functional group introduction into the side chain of the polymer (A) for example, a group having a siloxane bond represented by the following general formula (2) for the purpose of improving ink falling property and UV ozone resistance. (Hereinafter sometimes referred to as group (2)) can be introduced into the side chain of the polymer (A).
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group which may be substituted with a fluorine atom;
  • R 3 is a hydrogen atom or a carbon number; Represents an organic group of 1 to 10 and n represents an integer of 1 to 200.
  • R 1 and R 2 may be the same or different for each structural unit.
  • R 1 and R 2 are alkyl groups, the preferred carbon number is 1 to 10, and the more preferred carbon number is 1 to 6. These may have a linear structure or a branched structure.
  • R 1 and R 2 are cycloalkyl groups, the preferred carbon number is 3 to 10, and the more preferred carbon number is 5 or 6.
  • R 1 and R 2 are aryl groups, the preferred carbon number is 6-15, and the more preferred carbon number is 6-10.
  • Some or all of the hydrogen atoms of R 1 and R 2 may be substituted with fluorine atoms.
  • R 1 and R 2 are each independently a hydrogen atom, a methyl group, or a trifluoromethyl group. or it is preferably phenyl group, and particularly preferably R 1 and R 2 of the total siloxane units are methyl groups.
  • R 3 is an organic group having 1 to 10 carbon atoms, R 3 may have a nitrogen atom, an oxygen atom, a fluorine atom, or the like.
  • R 3 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and more preferably a trifluoromethyl group. Or it is a methyl group.
  • n is preferably an integer of 2 to 100.
  • the polymer (A) has a side chain having the group (2)
  • one type of the group (2) may be used alone, or two or more types may be used in combination.
  • the content of the silicon atom derived from the group (2) in the polymer (A) is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass. When the content of silicon atoms is within this range, the above effect can be imparted to the polymer (A) without impairing the effect of the present invention.
  • the adjustment of the silicon atom content in the polymer (A) is as follows. When the polymer (A) is produced by polymerizing the raw material monomer, the raw material single amount of the monomer having the group (2) It is performed by appropriately adjusting the blending amount for the whole body.
  • the polymer (A) preferably further has a side chain having an acidic group.
  • the introduction of the side chain having an acidic group in the polymer (A) is performed for the purpose of improving developability.
  • the developer used for the development photosensitive composition is generally an alkaline developer, and the solubility of the polymer (A) in the developer is improved by introducing an acidic group.
  • the polymer (A) contained in the unexposed part of the coating film is removed by the developer.
  • the acidic group which a polymer (A) has in a side chain may be 1 type, or may be 2 or more types.
  • a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, etc. are mentioned.
  • the introduction of acidic groups to the side chain of the polymer (A) may be performed by introducing the end group R 13 of the polyoxyalkylene group (11).
  • the polymer (A) used for this invention when manufacturing a polymer (A) by superposition
  • the blending amount is appropriately adjusted so that the obtained polymer (A) has the following preferable acid value.
  • the polymer (A) preferably has an acid value of 100 mgKOH / g or less, more preferably 10 to 50 mgKOH / g.
  • the acid value is the mass [mg] of potassium hydroxide necessary to neutralize 1 g of the sample, and the unit is described as mgKOH / g in this specification.
  • the polymer (A) preferably further has a side chain having a functional group capable of undergoing a crosslinking reaction with a functional group included in the matrix constituting the partition wall by heat or light, such as an epoxy group, a mercapto group, or a hydroxyl group.
  • a functional group capable of undergoing a crosslinking reaction with a functional group included in the matrix constituting the partition wall by heat or light
  • these functional groups introduced into the polymer (A) can be used alone or in combination of two or more.
  • the introduction of these functional groups into the side chain of the polymer (A) may be carried out by introducing it into the terminal group R 13 of the polyoxyalkylene group (11).
  • the introduction of a hydroxyl group can also be performed by using R 13 as a hydrogen atom.
  • the photosensitive composition of the present invention contains a photocuring initiator (B) and a binder resin (C) in addition to the polymer (A). This binder resin (C) is cured by the action of the photocuring initiator (B) when exposed.
  • This binder resin (C) is cured by the action of the photocuring initiator (B) when exposed.
  • cured by pattern exposure is removed with a developing solution.
  • a combination of a binder resin (C) having an acidic group and an alkaline developer is usually used.
  • the partition matrix has these functional groups of the polymer (A) by post-baking treatment after exposure and development.
  • the polymer (A) is sufficiently fixed to the partition wall by thermally crosslinking with the acidic group derived from the binder resin (C).
  • the polymer (A) particularly at a portion where the polymer (A) on the upper surface of the partition wall is present at a high density. The two are heat-crosslinked to become more polymerized and are sufficiently fixed to the partition walls.
  • the polymer (A) has a mercapto group, it is sufficiently fixed to the partition wall by crosslinking with the ethylenically unsaturated double bond group derived from the binder resin (C) by post-baking treatment in the same manner as described above. The As a result, it is possible to prevent the polymer (A) from flowing out into or eluting from the partition wall, which is a concern when the ink is subsequently injected into the partition opening by inkjet.
  • the introduction of the side chain having a functional group crosslinkable with the functional group of the partition matrix into the polymer (A) is performed when the polymer (A) is produced by polymerizing raw material monomers as described later.
  • the blending amount of the monomer having a functional group and a functional group crosslinkable in the partition matrix with respect to the whole raw material monomer can be added to the polymer (A) without impairing the effect of the present invention. Is appropriately adjusted so that the blending amount can provide the effect of suppressing the outflow / elution of the polymer (A).
  • the polymer (A) used in the present invention has a structure having a side chain having the group (1) and a side chain having a polyoxyalkylene group such as the group (11).
  • a side chain having an acidic group a side chain having an acidic group, a side chain having a functional group that can be cross-linked by heat or light, etc. Examples thereof include a method of forming directly by a polymerization reaction or a method of forming by chemical conversion after the polymerization reaction.
  • the polymer (A) has a side chain having the essential group (1), a side chain having a polyoxyalkylene group such as the group (11), and a side chain optionally having the above groups by polymerization reaction.
  • a monomer having the group (1), a monomer having a side chain having a polyoxyalkylene group such as the group (11), and a monomer having the group (2) if necessary Body, monomer having an acidic group, monomer having a functional group crosslinkable with the functional group of the partition matrix, and / or other monomer may be copolymerized under appropriate conditions. .
  • copolymerization examples include alternating copolymerization, block copolymerization, random copolymerization and the like, and the copolymerization can be carried out by a conventionally known method.
  • the polymer (A) Is preferably a random copolymer obtained by copolymerization by random copolymerization.
  • a monomer which has the said group (1) used for manufacture of a polymer (A) it is preferable that it is a compound represented by following General formula (3). These may be used individually by 1 type, or may use 2 or more types together.
  • CH 2 CR 4 —COO—Y—CFXR f (3)
  • R 4 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, an etheric oxygen atom or a C 1-20 fluoro atom.
  • Y is a single bond or a divalent organic group having no fluorine atom having 1 to 6 carbon atoms
  • —CFXR f is a group corresponding to the group (1), ie, X is A hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, or a fluorine atom.
  • a preferred embodiment of —CFXR f in the compound (3) is the same as that described for the group (1).
  • Y which is a divalent organic group having no fluorine atom having 1 to 6 carbon atoms, represents —R 5 —, —R 5 —NR 6.
  • R 5 is an alkylene group having 1 to 6 carbon atoms
  • R 6 is a hydrogen atom or R 7 is a single bond or an alkylene group having 1 to 4 carbon atoms, provided that when R 6 is a methyl group, R 5 bonded to NR 6 has 1 to 5 carbon atoms. Etc.).
  • R 5 -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 )-and the like.
  • R 7 -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) — and the like.
  • Y in the compound (3) is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
  • R 4 a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a phenyl group, a benzyl group and the like are preferable, and a hydrogen atom, a fluorine atom, a chlorine atom, A methyl group or a trifluoromethyl group is more preferable.
  • R 4 is particularly preferably a hydrogen atom or a methyl group. That is, the compound (3) is particularly preferably (meth) acrylate.
  • the compound represented by the general formula (3) is particularly preferably (meth) acrylate in which —CFXR f is a perfluoroalkyl group having 4 to 6 carbon atoms and Y is an alkylene group having 2 to 4 carbon atoms.
  • Specific examples include 2- (perfluorohexyl) ethyl (meth) acrylate and 2- (perfluorobutyl) ethyl (meth) acrylate.
  • a monomer which has the said group (11) used for manufacture of a polymer (A) it is preferable that it is a compound represented by the following general formula (12) or (13). These may be used individually by 1 type, or may use 2 or more types together.
  • CH 2 CR 14 —COO— (W—O) q — (R 11 O) m (R 12 O) j R 13 (12)
  • CH 2 CR 14 —O— (W—O) q — (R 11 O) m (R 12 O) j R 13 (13)
  • R 14 is substituted with a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms.
  • Q is 0 or 1.
  • — (R 11 O) m (R 12 O) j R 13 is a group corresponding to the group (11).)
  • — (R 11 O) m (R 12 O) j R 13 in the compounds (12) and (13) is the same as that described for the group (11).
  • — (W—O) q — represents a single bond when q is 0.
  • — (W—O) q — is an organic group having an oxygen atom on the R 11 side.
  • W is preferably a divalent hydrocarbon group having 2 to 10 carbon atoms, such as an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 5 or 6 carbon atoms, or a cycloalkylene having 5 or 6 carbon atoms.
  • a cycloalkylene group-containing alkylene group having 6 to 10 carbon atoms in total and having an alkylene group having 1 to 2 carbon atoms on both sides or one side of the group is preferable.
  • W is the same alkylene group as R 11 (and when q is not 0, it is also the same alkylene group as R 12 ), q is regarded as 0.
  • R 14 in the compounds (12) and (13) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
  • — (W—O) — represents a straight chain structure other than R 11 O and R 12 O, a branched structure, a ring structure, a partially ring
  • An oxygen atom-terminated hydrocarbon group having 1 to 10 carbon atoms is preferred. More preferred is an oxygen atom-terminated hydrocarbon group having 3 to 8 carbon atoms.
  • Specific examples of the oxygen atom-terminated hydrocarbon group include CH 2 C 6 H 10 CH 2 O (wherein C 6 H 10 is a cyclohexylene group), CH 2 O, CH (CH 3 ).
  • W in the compounds (12) and (13) is an oxyalkylene group having 3 or 4 carbon atoms (provided that when j is not 0, the same oxyalkylene as R 12 O, for ease of availability) Are preferred).
  • a hydrogen atom, a chlorine atom, a methyl group, a phenyl group, a benzyl group, and the like are preferable, and a hydrogen atom, a chlorine atom, or a methyl group is more preferable. preferable.
  • BLEMMER PME-400 (trade name, manufactured by NOF Corporation, CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, and the value of k is It is about 9.
  • NK ester M-230G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, k The value of is about 23).
  • New Frontier NF biisomer PEM6E (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k H: where k is about 6).
  • Light ester 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., CH 2 ⁇ CHCOO (CH 2 CH 2 O) k CH 3 : where k is about 9).
  • BLEMMER AE-400 (trade name, manufactured by NOF Corporation, CH 2 ⁇ CHCOO (CH 2 CH 2 O) k H: where k is about 10).
  • BLEMMER 70PEP-350B (trade name, manufactured by NOF Corporation, CH 2 ⁇ C (CH 3 ) COO (C 2 H 4 O) m (C 3 H 6 O) j H: where m is about 5, j is About 2).
  • BLEMMER 55PET-800 (trade name, manufactured by NOF Corporation, CH 2 ⁇ C (CH 3 ) COO (C 2 H 4 O) m (C 4 H 8 O) j H: wherein m is about 10, j is About 5).
  • the monomer having the group (2) used as necessary for the production of the polymer (A) is preferably a compound represented by the following general formula (4). These may be used alone or in combination of two or more.
  • R 8 is a hydrogen atom or a methyl group
  • Z is a single bond or a divalent organic group having 1 to 6 carbon atoms. It also has a siloxane bond bonded to Z.
  • the group is a group corresponding to the group (2), that is, R 1 and R 2 are each independently a hydrogen atom, an alkyl group optionally substituted with a fluorine atom, a cycloalkyl group, or An aryl group
  • R 3 is a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • n is an integer of 1 to 200.
  • R 1 , R 2 , R 3 and n in the compound (4) are the same as those described for the group (2).
  • the compound (4) has a divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, —CH 2 —, —CH 2 CH 2 -, -CH (CH 3 )-, -CH 2 CH 2 CH 2- , -C (CH 3 ) 2- , -CH (CH 2 CH 3 )-, -CH 2 CH 2 CH 2 CH 2 -,- CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 ) — and the like can be mentioned.
  • —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, and —CH 2 CH 2 CH 2 CH 2 — are preferable.
  • the monomer having an acidic group used as necessary for the production of the polymer (A) is not particularly limited as long as it has an acidic group.
  • a monomer having a carboxyl group, a phenolic hydroxyl group may be used.
  • a monomer having a sulfonic acid group may be used alone or in combination of two or more.
  • Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
  • Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and one or more hydrogen atoms of these benzene rings, such as a methyl group, an ethyl group, and an n-butyl group. And an alkyl group, a methoxy group, an ethoxy group, an n-butoxy group or the like, a halogen atom, a haloalkyl group having one or more halogen atoms, a nitro group, a cyano group, a compound substituted with an amide group, etc. .
  • Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, 2-methacrylic acid 2-sulfoethyl, Examples include 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, and the like.
  • crosslinkable functional group Monomer having a functional group that can be cross-linked by heat or light with the functional group of the partition matrix used as necessary for the production of the polymer (A).
  • crosslinkable functional group it will not be specifically limited. Specific examples include a monomer having an epoxy group and a monomer having a hydroxyl group. These may be used alone or in combination of two or more. In addition, it is preferable that the monomer which has a crosslinkable functional group does not have group (1) and group (2) substantially.
  • Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
  • Examples of the monomer having a hydroxyl group include 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) acrylate Amide, N, N-bis (hydroxymethyl) (meth) acrylamide.
  • thiocarboxylic acid ester can be introduce
  • the thiocarboxylic acid ester compound is, for example, a compound in which the carboxyl group of thioacetic acid, thiopropionic acid, thiobutyric acid, or thiobenzoic acid is substituted with a —COSH group.
  • Monomers other than those that can be optionally used for the production of the polymer (A) include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters. , (Meth) acrylic acid esters, (meth) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes and the like, and considering the heat resistance of the partition wall, (meth) acrylic acid esters, or ( Meth) acrylamides are preferred. Note that these compounds may have a functional group such as a carbonyl group or an alkoxy group.
  • monomers used for polymerization are appropriately selected from the monomers described above and copolymerized at an appropriate ratio.
  • the preferable compounding ratio of the various monomers used when manufacturing a polymer (A) is as follows.
  • the ratio of the monomer mass having the group (1) to the total mass of the monomer to be copolymerized is such that the fluorine atom content in the polymer (A) is in the above preferred range, specifically 20 to 50% by mass, The proportion is more preferably 25 to 42% by mass, particularly preferably 25 to 35% by mass. Although it depends on the type of the monomer having the group (1) as such a ratio, specifically, it is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, It is particularly preferably 40 to 60% by mass. If this ratio is too low, sufficient fluorine atom content cannot be secured, and sufficient development resistance tends to be not obtained, and in the vicinity of the upper surface of the partition formed using the photosensitive composition of the present invention.
  • a polymer (A) becomes difficult to transfer, and as a result, the liquid repellency of the upper surface of a partition may become inadequate.
  • this ratio is too high, the fluorine atom content exceeds the preferred range, the polymers (A) tend to self-aggregate, and as a result, the liquid repellency of the upper surfaces of the partition walls may be insufficient. . Furthermore, the adhesion between the partition walls and the substrate may be reduced.
  • the resulting polymer (A) when a monomer containing a fluorine atom is used as a raw material monomer in addition to the monomer having the group (1), the resulting polymer (A) What is necessary is just to adjust suitably the ratio of each raw material monomer so that fluorine atom content may become the said preferable range.
  • the ratio of the monomer mass having the group (11) to the total mass of the monomer to be copolymerized is such that the content of the group (11) in the polymer (A) is 5 to 60% by mass. It is preferable to do.
  • the ratio is more preferably 10 to 55% by mass, and particularly preferably 15 to 50% by mass.
  • the content of the group (11) in the polymer (A) is generally within the above preferred range, and liquid repellency is maintained even when a jet rinsing step using high-pressure water after the development step is performed. be able to. Furthermore, the generation of a residual film can be prevented.
  • the ratio of the monomer mass having the group (2) to the total mass of the monomer to be copolymerized is: It is preferable that the silicon (A) content in the polymer (A) is in the above preferred range, specifically 0.1 to 25% by mass, more preferably 0.5 to 20% by mass. Such a ratio depends on the type of the monomer having the group (2), but specifically, it is preferably 0.5 to 30% by mass, more preferably 2 to 20% by mass.
  • the silicon atom content in the polymer (A) is generally within the above preferable range, and the ink fall resistance and UV ozone resistance are improved. Good properties and the like.
  • the ratio of the mass of the monomer having an acidic group to the total mass of the monomer to be copolymerized is determined by the polymer ( It is preferable that the acid value of A) be in the above-mentioned preferable range, specifically 100 mgKOH / g or less, more preferably 10 to 50 mgKOH / g. Such a ratio depends on the type of monomer having an acidic group, but is specifically preferably 2 to 20% by mass, more preferably 4 to 12% by mass.
  • the proportion of the monomer having an acidic group in all the monomers to be copolymerized is within this range, the development of the unexposed portion can be carried out satisfactorily without impairing the effects of the present invention, and the parent of the opening can be performed. Although liquidity can be improved, it is favorable.
  • the ratio of the monomer mass having the crosslinkable functional group to the total mass of the monomer to be copolymerized Is preferably 1 to 40% by mass, and more preferably 5 to 20% by mass.
  • the ratio of the monomer having a crosslinkable functional group in all the monomers to be copolymerized is within this range, the polymer (A) can be immobilized on the partition wall without impairing the effects of the present invention. In addition, developability is improved.
  • the ratio of the mass of the other monomers to the total mass of the monomers to be copolymerized is 70% by mass or less. It is preferable that the content is 50% by mass or less. When the ratio of this mass exceeds 70 mass%, alkali developability may fall.
  • the polymer (A) used in the present invention has, as essential components, a side chain having the above group (1) and a side chain having a polyoxyalkylene group such as the above group (11).
  • a monomer having a polyoxyalkylene group such as a monomer having a group (2), a monomer having an acidic group, a monomer having a thermally crosslinkable functional group, and / or It can synthesize
  • a chain transfer agent as needed.
  • the adjustment of the mass average molecular weight of the polymer (A) can be performed by adjusting the conditions such as the polymerization temperature and time, the amount of the polymerization initiator, the addition amount of the chain transfer agent, and the like.
  • the polymer (A) thus produced is random copolymerization, but the block copolymer is prepared using a usual method such as changing the introduction timing of the raw material monomer into the copolymerization reaction system depending on the type of monomer. It is also possible to produce a polymer.
  • Examples of the solvent used for the polymerization of the polymer (A) include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Cellsorbs such as methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol Methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate Esters such as glycerol triacetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether.
  • polymerization initiator examples include known organic peroxides, inorganic peroxides, azo compounds and the like. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with a reducing agent. These polymerization initiators may be used alone or in combination of two or more.
  • organic peroxide examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl- ⁇ -cumyl peroxide and the like.
  • inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like.
  • Examples of the azo compound include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2 -Amidinopropane) dihydrochloride and the like.
  • chain transfer agents examples include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol; chloroform, carbon tetrachloride, tetraodor Alkyl halides such as carbon halides, and the thiocarboxylic acid ester compounds mentioned in the introduction of the mercapto group into the polymer (A).
  • mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol
  • chloroform carbon tetrachloride
  • the side chain having the above various groups in the polymer (A) used in the present invention in particular, the side chain having an acidic group or the side chain having a thermally crosslinkable functional group is also formed by chemical conversion after the polymerization reaction.
  • a copolymer having a side chain having the group (1) and a side chain having a hydroxyl group is produced by the above polymerization, and a polybasic acid anhydride (such as maleic anhydride) is reacted with the hydroxyl group of the copolymer.
  • a polymer (A) having a side chain having a carboxyl group as an acidic group can be produced.
  • the polymer (A) is preferably contained at a ratio of 0.07 to 1% by mass with respect to the total solid content of the composition. More preferably, it is contained in a proportion of 0.5% by mass. If the content is too small, the liquid repellency of the upper surface of the partition formed using the photosensitive composition of the present invention may be insufficient. If the content is too large, the adhesion between the partition and the substrate may be insufficient. May decrease.
  • action to a partition other than the said polymer (A).
  • a component has a side chain having a group represented by the general formula (2) and a side chain having a polyoxyalkylene group, and is represented by the general formula (1).
  • the polymer (A) ′ is a polymer essentially having a side chain having the group (2) instead of the side chain having the group (1) in the polymer (A).
  • polymer (A) ' in addition to the side chain which has group (1), although the structure was described about the polymer (A) which has a side chain which has group (2), polymer (A) ' Can have the same configuration as that except that it does not have a side chain having the group (1).
  • the silicon atom content in the polymer (A) ′ is preferably 0.1 to 25% by mass, and more preferably 0.5 to 20% by mass.
  • the photosensitive composition of the present invention can be imparted with an effect of enhancing the liquid repellency of the partition wall surface obtained by using the photosensitive composition of the present invention without impairing the effects of the present invention. It becomes possible.
  • the polymer (A) ′ has a side chain having the group (11), preferably the content of the group (11) with respect to the polymer (A) ′ is 5 to 60% by weight. Have in proportions.
  • the polymer (A) ′ can optionally have a side chain having an acidic group, a side chain having a functional group that can be cross-linked by heat or light with a functional group that the partition matrix has, such as Also for the polymerization reaction for forming a structure having a side chain, the monomer having the group (1) is not used as a raw material monomer, but the monomer having the group (2) is used as an essential raw material monomer. Except for the above, it can be the same as the polymer (A).
  • the polymer (A) ′ when the polymer (A) ′ is used, it is contained in a proportion of 0.5 to 30% by mass with respect to the total solid content of the composition. It is preferably contained in a proportion of 2 to 20% by mass. By using in this content, it becomes possible to give the photosensitive composition of the present invention the effect of enhancing the liquid repellency of the partition wall surface obtained by using the photosensitive composition of the present invention without impairing the effects of the present invention. Further, when the polymer (A) ′ is used, even if the polymer (A) having no side chain having the group (2) is used as the polymer (A) used in combination therewith, the same as described above. The effect can be demonstrated.
  • Photocuring initiator (B) (Photopolymerization initiator (B1))
  • a photopolymerization initiator (B1) that generates radicals upon irradiation with light is used as the photocuring initiator (B).
  • the photopolymerization initiator (B1) is not particularly limited as long as it is a compound that generates radicals upon irradiation with light.
  • ⁇ -diketones such as benzyl, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone
  • acyloins such as benzoin
  • acylo such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether
  • Inethers thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4 Thioxanthones such as sul
  • the photopolymerization initiator (B1) used in the present invention is preferably a compound represented by the following general formula (5).
  • R 21 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 an alkyl group.
  • R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms that is substituted or substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a 7 to 20 carbon atom that is substituted or unsubstituted with an alkyl group a benzoyl group, a phenoxycarbonyl group alkoxycarbonyl group or an alkyl group substituted or unsubstituted 7 to 20 carbon atoms having a carbon number of 2 ⁇ 12, R 23 is an alkyl group having 1 to 12 carbon atoms There, R 24, R 25, R 26 and R 27 each independently represent a hydrogen atom, an alkyl group having 1 to 12
  • R 21 is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms substituted or unsubstituted with an alkyl group, such as a methyl group
  • an alkyl group such as a methyl group
  • Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group.
  • an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.
  • R 22 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
  • R 22 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
  • an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
  • examples of the alkyl group having 1 to 12 carbon atoms represented by R 23 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
  • an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
  • R 24 , R 26 and R 27 are preferably hydrogen atoms.
  • R 25 is a benzoyl group having 7 to 20 carbon atoms substituted or unsubstituted with an alkyl group or a carbon number having 7 to 20 carbon atoms substituted or unsubstituted with an alkyl group.
  • a benzylcarbonyl group is preferable, and a 2-methylbenzoyl group, a benzylcarbonyl group, or a 1,3,5-trimethylbenzylcarbonyl group is particularly preferable.
  • the compound represented by the general formula (5) (O-acyloxime compound) is not particularly limited, but in the general formula (5), R 21 is a phenyl group, R 22 is an octyl group, and R 23 is an ethyl group.
  • R 24 , R 26 and R 27 are hydrogen atoms, R 25 is a benzoyl group;
  • R 21 is a methyl group,
  • R 22 is a butyl group, heptyl group or octyl group,
  • R 23 is an ethyl group,
  • R 24 , R 26 and R 27 are hydrogen atoms and
  • R 25 is a benzoyl group;
  • R 21 is a phenyl group, R 22 is an octyl group, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and
  • R 25 is compound 2-methylbenzoyl group;
  • R 21 is a methyl group,
  • R 22 is a methyl group or an octyl group,
  • R 23 is ethyl,
  • R 24, R 26 and R 27 are hydrogen atoms,
  • R 5 is a 2-methylbenzoyl group compound;
  • R 21 and R 22 is
  • a commercially available product can be used as the photopolymerization initiator (B1).
  • Examples of commercially available products include OXE02 (trade name, manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl) Oxime): a compound in which, in the above general formula (5), R 21 and R 22 are methyl groups, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is a 2-methylbenzoyl group) Is mentioned.
  • the content of the photopolymerization initiator (B1) in the radical curable photosensitive composition according to the present invention is preferably 1 to 15% by mass with respect to the total solid content of the composition, and 2 to 7% by mass. Is more preferable. When the content is 1 to 15% by mass, the curability is good and a pattern or line width close to the mask pattern can be formed by exposure and development.
  • Binder resin (C) (Photosensitive resin (C1))
  • the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond that is polymerized by the radical generated by the photopolymerization initiator (B1). Resin (C1) is used. Since the photosensitive resin (C1) has an ethylenic double bond involved in the photopolymerization in one molecule and further has an acidic group, the photosensitive resin (C1) is an uncured photosensitive composition using an alkaline developer. Unexposed portions can be selectively removed, and as a result, barrier ribs can be formed. In addition, it is preferable that photosensitive resin (C1) does not have group (1) and group (2) substantially.
  • an acidic group which the photosensitive resin (C1) has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, You may use 2 or more types together.
  • the photosensitive resin (C1) has, the double bond which addition polymerization groups, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, is mentioned, Two or more kinds may be used in combination.
  • addition polymerization groups such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group.
  • Two or more kinds may be used in combination.
  • some or all of the hydrogen atoms of these addition polymerizable groups may be substituted with a hydrocarbon group, preferably a methyl group.
  • the photosensitive resin (C1) is not particularly limited. Specifically, the resin (C1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin having ethylenic properties. Examples thereof include a resin (C1-2) into which a double bond and an acidic group are introduced. These may be used alone or in combination of two or more.
  • Resin (C1-1) is, for example, a side chain having a reactive group obtained by copolymerizing a monomer having a reactive group such as a hydroxyl group, a carboxyl group, or an epoxy group with a monomer having an acidic group. And a copolymer having an acidic group-containing side chain, a functional group capable of bonding to the reactive group, and a compound having an ethylenic double bond dissolved in a solvent and reacted. it can.
  • the monomer having a phosphate group as an acidic group is not particularly limited, and examples thereof include 2- (meth) acryloyloxyethane phosphoric acid.
  • Resin (C1-2) can be synthesized, for example, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond and then reacting with a polybasic carboxylic acid or its anhydride. Can do. Specifically, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, the carboxyl group and the epoxy group of the epoxy resin react to introduce an ethylenic double bond. Next, a carboxyl group can be introduce
  • the epoxy resin is not particularly limited, but is 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, Examples include an epoxy resin having a biphenyl skeleton represented by the formula (6), an epoxy resin represented by the following general formula (7), an epoxy resin represented by the following general formula (8), and the like.
  • each hydrogen atom of the benzene ring is independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a substituent. It may be substituted with a phenyl group which may have
  • 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 t is 0 to 10) .
  • each hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group. 0 to 10)
  • the epoxy resin represented by General formula (6), General formula (7), or General formula (8) and the compound which has a carboxyl group and an ethylenic double bond react, it is polybasic carboxylic acid.
  • the anhydride is reacted, it is preferable to use a mixture of a dicarboxylic acid anhydride and a tetracarboxylic dianhydride as the polybasic carboxylic acid anhydride.
  • the molecular weight can be controlled by changing the ratio of the dicarboxylic anhydride and the tetracarboxylic dianhydride.
  • a commercially available product can be used as the resin (C1-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin.
  • Examples of such commercially available products are KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H.
  • a resin obtained by introducing an acidic group and an ethylenic double bond into an epoxy resin represented by formula (7), or an acid group and an ethylenic double bond introduced into an epoxy resin represented by formula (8) Resin is preferred.
  • the resin more black colorant can be blended in the composition, and the light shielding property and optical density can be increased.
  • the coating film peeling at the time of image development is suppressed and a high resolution pattern can be obtained.
  • the linearity of the line is good and preferable.
  • the appearance after the post-baking step is maintained, and a smooth coating surface is easily obtained, which is preferable.
  • the photosensitive resin (C1) used in the present invention preferably has a mass average molecular weight of 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , more preferably 2.0 ⁇ 10 3 to 15 ⁇ 10 3 .
  • mass average molecular weight is less than 1.5 ⁇ 10 3 , curing during exposure may be insufficient, and when it exceeds 30 ⁇ 10 3 , developability may be deteriorated.
  • the number of ethylenic double bonds that the photosensitive resin (C1) has is preferably 3 or more, more preferably 6 or more in one molecule on average.
  • the number of ethylenic double bonds is 3 or more, the difference in alkali solubility between the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
  • the photosensitive resin (C1) preferably has an acid value of 10 to 300 mgKOH / g, more preferably 30 to 150 mgKOH / g. When it is 10 to 300 mgKOH / g, the developability of the photosensitive composition is good.
  • the content of the photosensitive resin (C1) in the radical curable photosensitive composition according to the present invention is preferably 5 to 80% by mass with respect to the total solid content of the composition, and is 10 to 60% by mass. Is more preferable. When the content is 5 to 80% by mass, the developability of the photosensitive composition is good.
  • the radical curable photosensitive composition according to the present invention comprises the polymer (A), a photopolymerization initiator (B1) as a photocuring initiator (B), and a binder resin (C).
  • the photosensitive resin (C1) having an acidic group and an ethylenic double bond as an optional component is described below for the purpose of improving various functions and the like as long as the effects of the present invention are not impaired. It is possible to contain components.
  • the radical curable photosensitive composition according to the present invention preferably contains a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing.
  • a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing.
  • the crosslinking agent (D) having two or more ethylenic double bonds is not particularly limited, but a compound having 2 to 10 (meth) acryloyloxy groups is preferable. Specifically, 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 hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate And urethane acrylate.
  • a commercially available product can be used as the crosslinking agent (D) having two or more ethylenic double bonds.
  • examples of such 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-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) , Ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name) Manufactured by Maruzen Petrochemical Co., Ltd., bis ⁇ 4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicar
  • 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. A-9300, BANI-M and BANI-X are preferable from the viewpoint of imparting hardness to the coating film and suppressing thermal sagging.
  • A-9300-1CL is preferable from the viewpoint of imparting flexibility to the coating film.
  • Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.
  • the content of the crosslinking agent (D) in the radical curable photosensitive composition according to the present invention is preferably 1 to 50% by mass with respect to the total solid content of the composition, and preferably 5 to 30% by mass. More preferred. When the content is 1 to 50% by mass, the developability of the photosensitive composition is improved.
  • Black colorant (E) The radical curable photosensitive composition according to the present invention has a black colorant (E) according to the required optical density of the partition wall when the cured product is used in applications requiring light shielding properties such as a black matrix. It is preferable to contain.
  • the black colorant (E) is not particularly limited, and examples thereof include carbon black, aniline black, anthraquinone black pigment, metal oxide such as titanium black, metal particles such as silver tin alloy, and perylene black pigment. Specifically, C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned.
  • the black colorant (E) may be a mixture of organic pigments such as red pigments, blue pigments, green pigments, and inorganic pigments. Among these, carbon black is preferable in consideration of the light shielding property. Carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust the color tone of the black colorant (E), carbon black can be used in combination with a blue pigment or a purple pigment.
  • the carbon black used as the black colorant (E) preferably has a specific surface area of 50 to 200 m 2 / g by the BET method. If this specific surface area is too small, the shape of the partition wall may be deteriorated. If the specific surface area is too large, the dispersion aid described later will be excessively adsorbed on the black colorant (E), resulting in a large amount of dispersion aid. It may be necessary to add an agent.
  • the carbon black used as the black colorant (E) has an oil absorption of dibutyl phthalate of 120 cc / 100 g or less, and a smaller amount is more preferable.
  • the carbon black used as the black colorant (E) preferably has an average primary particle diameter of 20 to 50 nm. If this average primary particle size is too small, it becomes difficult to disperse at a high concentration, it may be difficult to obtain a photosensitive composition with good stability over time, and if the average primary particle size is too large, It may cause deterioration of the shape of the partition wall.
  • the carbon black preferably has an average secondary particle size of 80 to 200 nm. The particle size of carbon black can be measured using a transmission electron microscope.
  • the black colorant (E) in the case where the black colorant (E) is blended in order to impart light-shielding properties such as a black matrix to the cured film.
  • the content depends on the required light shielding properties and optical density, but is preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and more preferably 25 to 40% by mass based on the total solid content of the composition. % Is particularly preferred. If this content is too small, the optical density of the partition may be insufficient in the case of a black matrix or the like. If the content is too high, the curability of the photosensitive composition will be reduced and the appearance of the partition will be reduced. Liquid repellency may be reduced.
  • the radical curable photosensitive composition according to the present invention contains a dispersible material such as the black colorant (E), it is preferable to contain a polymer dispersant in order to improve the dispersibility.
  • the polymer dispersant is not particularly limited, and is urethane type, polyimide type, alkyd type, epoxy type, polyester type, melamine type, phenol type, acrylic type, polyether type, vinyl chloride type, vinyl chloride vinyl acetate type. Examples thereof include a polymer system, a polyamide system, and a polycarbonate system. Among these, urethane type or polyester type is preferable.
  • the polymer dispersant may have a polyoxyethylene group and / or a polyoxypropylene group.
  • the polymer dispersant When the polymer dispersant is used for dispersing the black colorant (E), it is preferable to use a polymer dispersant having a basic group in consideration of the affinity for the black colorant (E). Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
  • Disparon DA-7301 (trade name, manufactured by Enomoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all above). Trade names, manufactured by BYK-Chemie), Solspers 5000, Solspers 17000 (all of which are trade names, manufactured by Zeneca).
  • the addition amount of the polymer dispersant is preferably 5 to 30% by mass and more preferably 10 to 25% by mass with respect to the dispersible material such as the black colorant (E). If the amount added is too small, the effect of improving dispersibility may be insufficient, and if the amount added is too large, the developability of the photosensitive composition may be lowered.
  • the radical curable photosensitive composition according to the present invention may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as a dispersion aid.
  • the dispersion aid is considered to have a function of improving dispersion stability by adsorbing to a dispersible material such as a black colorant (E) and a polymer dispersant.
  • the radical curable photosensitive composition according to the present invention may contain fine particles as necessary. Thereby, it can suppress that the shape of a partition changes at the time of the post-baking mentioned later.
  • the fine particles are not particularly limited, inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO); organic fine particles such as polyethylene and polymethyl methacrylate (PMMA) Is mentioned.
  • the fine particles are preferably inorganic fine particles in view of heat resistance, and silica or zirconia is preferred in consideration of availability and dispersion stability.
  • the photosensitive composition contains a black colorant (E) and a polymer dispersant in order to improve the dispersibility thereof, the fine particles can be obtained by considering the adsorptive capacity of the polymer dispersant. It is preferably negatively charged.
  • the fine particles do not absorb light irradiated at the time of exposure, i-line (365 nm), h-line (405 nm), which is the main emission wavelength of an ultra-high pressure mercury lamp, It is particularly preferable not to absorb g-line (436 nm).
  • the particle diameter of the fine particles is preferably 1 ⁇ m or less, more preferably 200 nm or less, since the surface smoothness of the partition wall is improved.
  • the content of fine particles in the radical curable photosensitive composition according to the present invention is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, based on the total solid content of the composition. If the content is too small, the shape of the partition wall may change during post-baking, and if the content is too large, the dispersion stability of the photosensitive composition may decrease.
  • the radical curable photosensitive composition according to the present invention may contain a silane coupling agent as required. Thereby, the adhesiveness of a partition and a board
  • the silane coupling agent is not particularly limited. Specifically, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyl Examples include trimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, polyoxyalkylene having a triethoxysilyl group, and imidazolesilane. Good.
  • the radical curable photosensitive composition according to the present invention may contain a thermosetting agent, if necessary. Thereby, the heat resistance of a partition and water permeability resistance can be improved. Further, when the polymer (A) has a thermally crosslinkable functional group, the polymer (A) and the thermosetting agent are chemically bonded, thereby obtaining an effect of fixing the polymer (A) to the partition wall. It is done.
  • thermosetting agent Amino resin (melamine compounds, such as hexamethoxymethylol melamine), a compound which has two or more epoxy groups, a compound which has two or more hydrazino groups, a polycarbodiimide compound, an oxazoline group
  • Amino resin melamine compounds, such as hexamethoxymethylol melamine
  • a compound which has two or more epoxy groups a compound which has two or more hydrazino groups
  • a polycarbodiimide compound an oxazoline group
  • a compound having two or more, a compound having two or more aziridine groups, a polyvalent metal, a compound having two or more mercapto groups, a polyisocyanate compound and the like may be mentioned, and two or more may be used in combination.
  • amino resins, compounds having two or more epoxy groups, or compounds having two or more oxazoline groups are preferable.
  • the radical curable photosensitive composition according to the present invention may contain a phosphate compound as necessary. This is preferable because adhesion to the substrate can be improved.
  • the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
  • the radical curable photosensitive composition according to the present invention includes a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, as necessary, in addition to various components other than those described above.
  • An ultraviolet absorber or the like may be included.
  • the radical curable photosensitive composition according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. can do.
  • the photosensitive composition of the present invention is an acid curable type
  • the photosensitive composition comprises a polymer (A) and a photoacid generator (B) as a photocuring initiator (B).
  • B2) and an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group as the binder resin (C), and a compound having two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group Contains a crosslinkable resin (C22).
  • an acid is generated from the photoacid generator (B2) in the light irradiation portion during exposure in photolithography or the like, and an alkali-soluble resin having a carboxyl group and / or a phenolic hydroxyl group ( C21) and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group undergo a crosslinking reaction to form a cured coating film.
  • the polymer (A) contained in the acid-curable photosensitive composition according to the present invention is a characteristic component in the photosensitive composition of the present invention, and includes the above-described radical curable photosensitive composition including preferred embodiments thereof.
  • the polymer (A) described in the article can be applied to the acid-curable photosensitive composition.
  • the content of the polymer (A) in the photosensitive composition can also be the same as described above.
  • the polymer (A) ′ described above as a component capable of imparting a liquid repellency to the partition walls can be used in the same manner as in the case of the radical curable photosensitive composition.
  • Photocuring initiator (B) (photoacid generator (B2))
  • a photoacid generator (B2) that is a compound that generates an acid by light is used as the photocuring initiator (B).
  • the photoacid generator (B2) include diaryliodonium salts, triarylsulfonium salts, triazine compounds, sulfonyl compounds, sulfonic acid esters, and the like.
  • diaryliodonium salt examples include diphenyliodonium, 4-methoxyphenylphenyliodonium, bis (4-t-butylphenyl) iodonium, and the like.
  • the anion moiety of the diaryliodonium salt include trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate, pentafluorobenzenesulfonate, hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate, (R f ) k PF (6-k) ⁇ (where k is an integer of 1 to 6) and the like.
  • the diaryliodonium salt consists of a combination of one of the cation moieties and one of the anion moieties.
  • An example is bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate.
  • the cation moiety of the triarylsulfonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, diphenyl-2,4,6-trimethylphenylsulfonium, and the like.
  • Specific examples of the anion moiety of the triarylsulfonium salt include specific examples of the anion moiety of the diaryl iodonium salt.
  • a triarylsulfonium salt consists of a combination of one of the cation moieties and one of the anion moieties. Examples thereof include triphenylsulfonium trifluoromethanesulfonate.
  • triazine compounds include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (2-furyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine, 2- (5-methyl-2-furyl) ethenyl-bis (trichloromethyl)- Examples include 1,3,5-triazine and 2- (3,4-dimethoxyphenyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine.
  • sulfonyl compound examples include bis (phenylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like.
  • sulfonic acid esters include 2-nitrobenzyl p-toluenesulfonate, ⁇ - (p-toluenesulfonyloxyimino) -phenylacetonitrile, and the like.
  • the content of the photoacid generator (B2) in the acid curable photosensitive composition according to the present invention is preferably 0.1 to 30% by mass, preferably 1 to 20% by mass, based on the total solid content of the composition. More preferred. Within this range, the developability of the photosensitive composition will be good.
  • Binder resin (C) (alkali-soluble resin (C21) / crosslinkable resin (C22))
  • the binder resin (C) includes a carboxyl group and / or a phenolic hydroxyl group that undergoes cross-linking polymerization by the action of the acid generated by the photoacid generator (B2).
  • Alkali-soluble resin (C21) The alkali-soluble resin (C21) has a carboxyl group and / or a phenolic hydroxyl group.
  • a crosslinkable resin (C22) which is a compound which is soluble in an alkaline solution by having a carboxyl group and / or a phenolic hydroxyl group, and which has two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group; It can be crosslinked to form a cured film.
  • the alkali-soluble resin (C21) can be used without any limitation as long as it is a resin that is soluble in an alkaline solution constituting a developer used in photolithography of the photosensitive composition.
  • These resins preferably have substantially no groups (1) and (2).
  • a resin (C21-1) obtained by polymerizing a monomer having a carboxyl group and an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond as an essential component is obtained by polymerizing the carboxyl group and ethylene. It can be obtained by copolymerizing a monomer having an ionic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond, if necessary, with another monomer.
  • the proportion of monomer units based on other monomers is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. Within this range, the alkali solubility and developability of the photosensitive composition are good.
  • the monomer having a carboxyl group and an ethylenic double bond used for preparing the alkali-soluble resin (C21-1) includes acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid. Examples include acids, fumaric acid, cinnamic acid, or salts thereof.
  • Examples of the monomer having a phenolic hydroxyl group and an ethylenic double bond include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like, in which one or more hydrogen atoms of these benzene rings are methyl, ethyl, Alkyl groups such as n-butyl, alkoxy groups such as methoxy, ethoxy and n-butoxy, halogen atoms, haloalkyl groups in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms, nitro groups, cyano groups, amide groups And the like.
  • the other monomer the same monomer as the other monomer used for the production of the polymer (A) can be used.
  • phenol resin examples include aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol and hydroquinone and phenols which are at least one selected from these alkyl-substituted or halogen-substituted aromatic compounds as aldehydes such as formaldehyde, acetaldehyde and benzaldehyde.
  • aldehydes such as formaldehyde, acetaldehyde and benzaldehyde.
  • a phenol / formaldehyde resin, a cresol / formaldehyde resin, or a phenol / cresol / formaldehyde cocondensation resin can be used.
  • the acid value of the alkali-soluble resin (C21) is preferably 10 to 600 mgKOH / g, more preferably 50 to 300 mgKOH / g. Within this range, the developability of the photosensitive composition will be good.
  • the number average molecular weight of the alkali-soluble resin (C21) is preferably 200 to 20000, more preferably 2000 to 15000. Within this range, the alkali solubility and developability of the photosensitive composition will be good.
  • the mass average molecular weight is preferably 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , and more preferably 2.0 ⁇ 10 3 to 15 ⁇ 10 3 . When the mass average molecular weight is less than 1.5 ⁇ 10 3 , curing during exposure may be insufficient, and when it exceeds 30 ⁇ 10 3 , developability may be deteriorated.
  • the content of the alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group is 10 to 90% by mass with respect to the total solid content of the composition. Preferably, 30 to 80% by mass is more preferable. Within this range, the developability of the photosensitive composition of the present invention is good.
  • the crosslinkable resin (C22) is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. By having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group, it can be crosslinked with an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group to form a cured coating film. Moreover, when the said polymer (A) has a carboxyl group and / or a hydroxyl group, it can also bridge
  • the crosslinkable resin (C22) is preferably a compound substantially free of the group (1) and the group (2).
  • the crosslinkable resin (C22) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, and oxazoline compounds. These may be used alone or in combination of two or more.
  • Amino resins include compounds in which a part or all of amino groups such as melamine compounds, guanamine compounds, urea compounds, etc. are hydroxymethylated, or part or all of the hydroxyl groups of the hydroxymethylated compounds are methanol, ethanol , A compound etherified with n-butyl alcohol, 2-methyl-1-propanol, and the like, for example, hexamethoxymethylmelamine and the like.
  • Epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol / novolak type epoxy resins, cresol / novolac type epoxy resins, trisphenol methane type epoxy resins, brominated epoxy resins and other glycidyl ethers, 3, Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, glycidyl such as diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate Esters, tetraglycidyldiaminodiphenylmethane, glycidylamines such as triglycidylparaaminophenol, and complex such as triglycidyl isocyanurate Such expression epoxy resin.
  • oxazoline compound examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl Mention may be made of copolymers of polymerizable monomers such as -4-methyl-2-oxazoline.
  • the content of the crosslinkable resin (C22), which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group is the total solid content of the composition.
  • the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. Within this range, the developability of the photosensitive composition will be good.
  • the acid curable photosensitive composition according to the present invention includes the polymer (A), a photoacid generator (B2) as a photocuring initiator (B), and a binder resin (C). And an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group, and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group.
  • various optional components can be contained for the purpose of improving various functions and the like within a range not impairing the effects of the present invention.
  • optional components include all components other than the crosslinking agent (D) having two or more ethylenic double bonds among the optional components described in the radical curable photosensitive composition.
  • the photosensitive composition it can be used for an acid-curable photosensitive composition.
  • the acid-curable photosensitive composition according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. can do.
  • a diluted solution obtained by diluting the photosensitive composition with a solvent is used. It is preferable to form a coating film of the photosensitive composition by volatilizing and removing the solvent after using it to form a coating film (wet film).
  • the solvent for diluting the photosensitive composition is not particularly limited. Specifically, alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2- Cellsorbs such as butoxyethanol and 2-propoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate; Ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether
  • the diluted solution obtained by diluting the photosensitive composition with a solvent is preferably prepared so that the concentration of the photosensitive composition, that is, the solid content concentration is 5 to 40% by mass, and is 10 to 25% by mass. It is more preferable to prepare.
  • the partition wall of the present invention is a partition wall formed by partitioning the substrate into a plurality of pixel forming sections by using the cured film of the photosensitive composition of the present invention. It can be applied to a black matrix of an organic EL element.
  • a diluted solution of the photosensitive composition of the present invention is applied to a substrate.
  • the substrate is not particularly limited, and various glass plates; SiC substrate, inorganic substrate such as silicon; inorganic oxide substrate such as ITO; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate And thermoplastic resin sheets such as polysulfone, polyimide, and poly (meth) acrylic resin; and cured sheets of thermosetting resin such as epoxy resin and unsaturated polyester.
  • the substrate is preferably a heat resistant resin such as a glass plate and polyimide.
  • the substrate is preferably transparent.
  • the substrate is a substrate in which an inorganic film such as an organic film or TFT (Thin Film Transistor), ITO, SiO 2 is formed on a transparent substrate such as a glass substrate, or a patterned substrate, silicon nitride Or a substrate on which an insulating film such as polyimide is formed, or a laminated substrate in which these substrates are laminated.
  • an inorganic film such as an organic film or TFT (Thin Film Transistor), ITO, SiO 2 is formed on a transparent substrate such as a glass substrate, or a patterned substrate, silicon nitride Or a substrate on which an insulating film such as polyimide is formed, or a laminated substrate in which these substrates are laminated.
  • the coating method is not particularly limited, and examples thereof include spin coating, spraying, slit coating, roll coating, spin coating, and bar coating.
  • the coating film formed on the substrate is dried. Thereby, since a solvent volatilizes, the coating film of the photosensitive composition without stickiness is obtained. It does not specifically limit as a drying method, Vacuum drying and heat drying are mentioned. In order to efficiently dry the coating film without causing uneven appearance, it is preferable to use vacuum drying and heat drying in combination.
  • the drying conditions vary depending on the type and composition of the components contained in the photosensitive composition, but the vacuum drying is preferably 10 to 500 Pa (absolute pressure) for 10 to 300 seconds, and the heat drying is 50 to 120. It is preferable that the temperature is 10 to 2000 seconds at ° C.
  • the coating film is exposed through a mask having a predetermined pattern.
  • the light irradiated at the time of exposure is not particularly limited, and visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 excimer laser, etc.
  • Excimer laser, X-ray, electron beam and the like can be mentioned.
  • Light having a wavelength of 100 to 600 nm is preferable, light having a wavelength of 300 to 500 nm is more preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable.
  • a well-known super high pressure mercury lamp etc. can be used as a light source.
  • Exposure is usually 5 ⁇ 1000mJ / cm 2 at i-line standard, preferably 10 ⁇ 400mJ / cm 2, more preferably 20 ⁇ 200mJ / cm 2, particularly preferably 50 ⁇ 100mJ / cm 2.
  • the exposure amount is less than 5 mJ / cm 2 , the coating film may be insufficiently cured and the developability may be deteriorated.
  • it exceeds 1000 mJ / cm 2 high resolution may not be obtained.
  • the developer is not particularly limited, and examples thereof include aqueous alkali solutions such as inorganic alkalis, amines, alkanolamines, and quaternary ammonium salts.
  • the development time that is, the time for contact with the developer is preferably 5 to 180 seconds.
  • the developing method is not particularly limited, and examples thereof include a liquid filling method, a dipping method, and a shower method.
  • Jet rinse process Furthermore, it is preferable to perform jet rinsing.
  • Jet rinsing is a process in which water is compressed or water and air are compressed and sprayed onto a substrate on which a partition wall is formed.
  • the pressure is preferably 2 to 20 MPa.
  • post-exposure may be performed on the developed partition wall.
  • the exposure may be performed from either the surface on which the partition is formed or the surface on which the partition is not formed, or may be performed from both surfaces.
  • the light irradiated during exposure is preferably ultraviolet light.
  • the light source a known ultra-high pressure mercury lamp, high-pressure mercury lamp, or the like can be used. These light sources generally emit light having a wavelength of 600 nm or less that contributes to hardening of the partition walls, and emit less light having a wavelength of 200 nm or less that causes oxidative decomposition of the partition walls. Furthermore, it is preferable that the quartz tube glass used for the light source has a function of an optical filter that cuts light having a wavelength of 200 nm or less.
  • Exposure is usually at 50 mJ / cm 2 or more, preferably 200 mJ / cm 2 or more, more preferably 1000 mJ / cm 2 or more, 2000 mJ / cm 2 or more is particularly preferable.
  • a low-pressure mercury lamp may be used as the light source.
  • the exposure amount is preferably 500 mJ / cm 2 or less, and 300 mJ / cm 2 or less. Is more preferable.
  • the heating condition is preferably 150 to 250 ° C. for 5 to 90 minutes, and the heating temperature is more preferably 180 ° C. or higher. If the heating temperature is too low, chemical resistance may be insufficient, and when ink is applied to the partition walls, the partition walls may swell or the ink may ooze. On the other hand, if the heating temperature is too high, the partition walls may be thermally decomposed.
  • a hot plate, an oven or the like can be used as the heating device.
  • the partition wall of the present invention is formed by curing the photosensitive composition of the present invention through the photolithography process as described above.
  • the black matrix which exhibits black can be comprised by mix
  • a black matrix will be formed by forming a partition using a photosensitive composition.
  • the partition wall of the present invention preferably has a width (average value) of 100 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the distance between adjacent partition walls, that is, the width (average value) of the openings is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the height (average value) of the partition walls is preferably 0.05 to 50 ⁇ m, more preferably 0.2 to 10 ⁇ m.
  • the liquid repellency (ink repellency) of the partition walls made of a cured film of the photosensitive composition includes water repellency and oil repellency, and water and PGMEA (propylene glycol monomethyl ether acetate: as a solvent for the ink, respectively) It can be evaluated by the contact angle of a commonly used organic solvent).
  • the upper surface of the partition wall of the present invention preferably has a water contact angle of 90 ° to 150 °, more preferably 95 ° to 120 °. Further, the upper surface of the partition wall preferably has a PGMEA contact angle of 35 ° to 55 °, more preferably 40 ° to 50 °.
  • the color filter of the present invention is a color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, and the partition is formed of the partition of the present invention.
  • the pixel is formed by an inkjet method.
  • the partition walls are preferably a black matrix having an optical density of about 2 to 7.
  • the color filter of the present invention is manufactured by forming a partition, for example, a black matrix on a substrate, and then forming a pixel by applying ink to the opening of the partition using an inkjet method. can do.
  • the ink jet method is not particularly limited, but is a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which intermittent ink is ejected using a piezoelectric element, and ink is heated and intermittently utilizing its foaming.
  • the method of injecting automatically is mentioned.
  • the arrangement of the pixels is not particularly limited, and examples thereof include known arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.
  • the ink mainly contains a coloring component, a binder resin component, and a solvent, and may be either water-based ink or oil-based ink.
  • a coloring component pigments and / or dyes excellent in heat resistance, light resistance and the like are preferable.
  • 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 as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin and / or a water-dispersible resin as a binder resin component.
  • the oil-based ink contains an organic solvent as a solvent, and a resin soluble in the organic solvent as a binder resin component.
  • a pixel after applying an ink to a partition, for example, an opening of a black matrix, using an inkjet method, a pixel can be formed by performing drying, heat curing, ultraviolet curing, or the like as necessary.
  • a protective film can be formed as necessary. Thereby, the surface smoothness of the color filter can be improved, and the eluent from the partition walls and pixels can be blocked from reaching the liquid crystal layer adjacent to the protective film.
  • a method for removing the liquid repellency on the upper surface of the partition wall is not particularly limited, and examples thereof include plasma ashing treatment and optical ashing treatment.
  • a photo spacer may be formed on a partition wall, for example, a black matrix, if necessary.
  • Organic EL Element is an organic EL element having a plurality of pixels and a partition located between adjacent pixels on a substrate, and the partition is formed of the partition of the present invention.
  • the pixel is formed by an inkjet method.
  • the organic EL device of the present invention can be produced as follows. First, using a sputtering method or the like, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate, and the transparent electrode is etched into a desired pattern as necessary.
  • a partition for example, a black matrix is formed on the substrate, and then a hole transport material is used as an ink in the opening of the partition (black matrix) using an ink jet method.
  • the solution of the above and the solution of the light emitting material are sequentially applied and dried to form a hole transport layer and a light emitting layer.
  • an organic EL element is obtained by forming an electrode, such as aluminum, using a vapor deposition method or the like to form a pixel.
  • V-65 V-65 (Wako Pure Chemical Industries, 2,2'-azobis (2,4-dimethylvaleronitrile))
  • Chain transfer agent n-DM: n-dodecyl mercaptan (solvent)
  • MEK 2-butanone
  • Photosensitive composition component photocuring initiator (B): photopolymerization initiator (B1)
  • OXE02 OXE02 (manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) (general formula (5) Wherein R 21 and R 22 are methyl groups, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is a 2-methylbenzoyl group)
  • EX1010 EX-1010 (manufactured by Nagase ChemteX Corporation, a resin solution in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the general formula (7), solid content: 70% by mass, mass average molecular weight: 3,020)
  • ZCR15 photocur
  • the column is maintained at 37 ° C., tetrahydrofuran is used as the eluent, the flow rate is 0.2 mL / min, and the 0.5 mass% tetrahydrofuran solution of the measurement sample is measured. 40 ⁇ L was injected.
  • ⁇ Fluorine atom content The fluorine atom content in the polymer was calculated from the charged value of the polymerization reaction.
  • the acid value is a theoretical value calculated from the blending ratio of monomers as raw materials.
  • Example 1 Polymer (A-1) (0.03 part) obtained in the above synthesis example, CB (31.6 parts) as a dispersion of black colorant (E), OXE02 as photopolymerization initiator (B1) (0.76 parts), EX1010 (6.3 parts) as a dispersion of the photosensitive resin (C1), DPHA (1.9 parts) as a crosslinking agent (D), and PGMEA (34.4 parts) as a solvent ) And cyclohexanone (25.0 parts) were mixed to obtain a diluted solution of the photosensitive composition.
  • the content of the polymer (A-1) in the total solid content of the diluted liquid of the photosensitive composition was 0.20% by mass.
  • a diluted solution of the photosensitive composition is applied on a glass substrate, and then dried on a hot plate at 100 ° C. for 2 minutes to form a coating film of the photosensitive composition having a thickness of 2.0 ⁇ m. did.
  • the coating film was irradiated with light having an exposure amount of 100 mJ / cm 2 on the basis of i-line (365 nm) through a mask to be exposed.
  • the mask has a lattice pattern with a light shielding portion of 150 ⁇ m ⁇ 400 ⁇ m and a light transmitting portion of 20 ⁇ m, and the volume of the opening formed is 120 pL.
  • the area of the pattern was 10 cm 2.
  • the developer used was a 10-fold diluted aqueous solution of semi-clean DL-A4 (trade name, manufactured by Yokohama Yushi Kogyo Co., Ltd.).
  • a nozzle whose irradiation angle to the substrate was narrowed to 8 degrees or less was used as a nozzle, and a developing solution was discharged onto the substrate under a pressure of 0.15 MPa to generate bubbles and spin development was performed. Thereafter, the unexposed portion was washed away with water and dried.
  • the glass substrate sample (1) of Example 1 in which the partition walls were formed was obtained by heating (post-baking) the glass plate in an oven at 220 ° C. for 30 minutes.
  • Examples 2 to 5 Photosensitivity containing each of the polymers (A-2) to (A-5) obtained in the above synthesis examples in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2.
  • Glass substrate samples (1) of Examples 2 to 5 in which partition walls made of a cured film of the composition were formed, and Examples 2 to 5 of which a cured product of the coating film of the photosensitive composition was formed The glass substrate sample (2) and the glass substrate sample (3) which performed jet rinse further were obtained.
  • the liquid repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured film of the glass substrate sample (2). Moreover, the liquid repellency tolerance by jet rinse was evaluated by measuring the contact angle of PGMEA of the surface of the coating-film hardened
  • the contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid come into contact, and is defined as an angle on the side including the liquid. For this reason, the larger the contact angle, the better the liquid repellency of the cured film.
  • ⁇ State of residual film generation> In the glass substrate sample (1), the number of development defects was visually measured to evaluate the state of residual film generation. The number of development defects per area was determined to be less than 100, ⁇ for 100 to less than 200, and x for 200 or more.
  • the mass average molecular weight (Mw (A)) is in the range of 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4
  • polyoxyalkylene Polymers (A-1) to (A-5) corresponding to the group-containing polymer (A) (the content of polyoxyalkylene groups in the polymer is preferably 5 to 60% by mass in the present invention)
  • the liquid repellency was good. This is because the polymer (A) was not peeled off from the surface layer even when the barrier ribs obtained using the photosensitive compositions of Examples 1 to 5 were subjected to high-pressure water washing called jet rinsing. Is maintained.
  • the ink wets into the openings between the partition walls. It expanded and there were no white spots. This indicates that in the coating films obtained from the photosensitive compositions of Examples 1 to 5, the developability was good and the polymer (A) component did not move from the partition wall surface to the opening between the partition walls. Is.
  • the weight average molecular weight of the polymer (A) was 40,000 or more.
  • the ink wets and spreads in the opening between the partition walls, and there is no white spot. It was.
  • a polymer (R-1) having a mass-average molecular weight Mw (A) outside the range of the polymer (A) according to the present invention specifically a mass-average molecular weight Mw of less than 2.6 ⁇ 10 4 is obtained.
  • the liquid repellency after jet rinsing was remarkably lowered. Further, when about 20 pL of ink was applied to the opening between the partitions having a volume of 120 pL, that is, when the amount of ink applied was small relative to the volume of the opening, there was a portion where the ink did not spread out in the opening.
  • the photosensitive composition of the present invention is an ink repellent component that does not have an ethylenic double bond, but has good ink repellency at the upper part of the partition wall, resistance to developer not corroded by the developer, residual film remaining without development It is a photosensitive composition containing an ink repellent component capable of imparting the property of suppressing the generation of ink and the good wetting and spreading property of the ink to the opening between the partition walls to the obtained partition wall.
  • Such a photosensitive composition of the present invention is suitably used for forming barrier ribs, for example, for manufacturing color filters using an inkjet recording technique and for manufacturing organic EL display elements.
  • a material for forming a permanent film such as a partition for partitioning each TFT of an organic TFT (Thin Film Transistor) array, a partition for an ITO electrode of a liquid crystal display element, a partition for a circuit wiring board.

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Abstract

La présente invention se rapporte à une composition photosensible contenant un composant repoussant l'encre qui peut former une paroi de séparation obtenue à partir de ce dernier présentant une bonne répulsion de l'encre au niveau de sa partie supérieure, une résistance au révélateur suffisante pour empêcher la corrosion par un révélateur liquide et des propriétés empêchant l'apparition d'un film qui reste, ainsi qu'une bonne mouillabilité et une bonne capacité d'étalement d'une encre sur une partie d'ouverture entre des parois de séparation bien que le composant repoussant l'encre ne présente pas une double liaison éthylique. De façon précise, la présente invention se rapporte à une composition photosensible qui contient : un polymère qui présente un poids moléculaire moyen en poids (Mw) de 2,6 × 104 < Mw ≤ 20 × 104 et contient une chaîne latérale ayant un groupe représenté par la formule générale (1) et une chaîne latérale ayant un groupe polyoxyalkylène mais pas de chaîne latérale ayant une double liaison éthylénique ; un initiateur de photodurcissement ; et une résine de liant. -CFXRf (1) (Dans la formule, X représente un atome d'hydrogène, un atome de fluor ou un groupe trifluorométhyle ; et Rf représente un atome de fluor ou un groupe fluoroalkyle ayant de 1 à 20 atomes de carbone et ayant, facultativement, un atome d'oxygène d'un éther.)
PCT/JP2010/073603 2009-12-28 2010-12-27 Composition photosensible, paroi de séparation, filtre coloré et élément électroluminescent organique WO2011081151A1 (fr)

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JP2011547696A JP5682573B2 (ja) 2009-12-28 2010-12-27 感光性組成物、隔壁、カラーフィルタおよび有機ｅｌ素子
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