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WO2019181954A1 - Composé polymérisable, polymère photodurcissable, film isolant, film de protection et dispositif à transistor organique - Google Patents

Composé polymérisable, polymère photodurcissable, film isolant, film de protection et dispositif à transistor organique Download PDF

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WO2019181954A1
WO2019181954A1 PCT/JP2019/011494 JP2019011494W WO2019181954A1 WO 2019181954 A1 WO2019181954 A1 WO 2019181954A1 JP 2019011494 W JP2019011494 W JP 2019011494W WO 2019181954 A1 WO2019181954 A1 WO 2019181954A1
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group
alkyl
formula
polymer
fluoroalkyl
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Japanese (ja)
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山川浩
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Tosoh Corp
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Tosoh Corp
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Priority claimed from JP2018128598A external-priority patent/JP7283035B2/ja
Priority claimed from JP2019044889A external-priority patent/JP7371334B2/ja
Priority claimed from JP2019044884A external-priority patent/JP7363060B2/ja
Application filed by Tosoh Corp filed Critical Tosoh Corp
Publication of WO2019181954A1 publication Critical patent/WO2019181954A1/fr
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]

Definitions

  • the present invention relates to a polymer for forming an insulating film and a protective film that can be solution-coated on an organic semiconductor layer included in an organic transistor device.
  • the present invention also relates to a polymer for forming an insulating layer included in an organic transistor device.
  • the present invention also relates to a polymer suitable for use in an electronic device.
  • a top gate type organic transistor device manufactured by a full printing method has a flattening layer or an insulating layer (A layer), a lower metal electrode (source, and the like) on a substrate such as a plastic film from the lower surface to the upper surface of the device.
  • a drain electrode), an organic semiconductor layer (B layer), an insulating layer (C layer), and an upper metal electrode (gate electrode) are formed in this order.
  • the organic semiconductor layer is locally formed in a shape covering the source electrode and the drain electrode, and the drain electrode has a shape drawn to the outside of the region where the organic semiconductor layer is formed, and is in contact with the C layer.
  • the C layer also serves as a protective film that reduces the influence of the organic semiconductor and the organic transistor device coming into contact with the outside air and deteriorating.
  • the A layer and the C layer are formed by printing a solution obtained by dissolving an insulating polymer in an organic solvent.
  • the polymer solution forming the C layer must not dissolve the already formed organic semiconductor layer (B layer). Further, it is necessary to form a contact hole in the C layer.
  • the contact hole is a hole for connecting the drain electrode under the C layer and the driving circuit of the transistor.
  • a method of forming the C layer on the upper surface of the B layer for example, a method of forming a polyparaxylylene (PPX) film by vapor deposition is known. Since this method does not use a solvent, the raw material is heated and vapor-deposited onto a substrate under vacuum to form a polyparaxylylene thin film, so that the organic semiconductor layer should not be dissolved by contact with the solvent. I can do it.
  • the PPX film does not dissolve in a general-purpose hydrocarbon solvent at room temperature, and has a fatal defect that it is difficult to form a contact hole.
  • the method of vapor deposition limits the size of the substrate that can be treated, and it is difficult to continuously manufacture by the entire printing process, and the batch process is inferior in economic efficiency.
  • a method in which a solution obtained by dissolving a fluorinated cyclic ether polymer in a fluorinated solvent is coated on the upper surface of the organic semiconductor layer is known. Since many of the currently known organic semiconductors do not dissolve in fluorine-based solvents, an insulating layer of a fluorine-based cyclic ether polymer can be formed on the organic semiconductor layer without affecting the organic semiconductor layer.
  • aliphatic alcohol is one of highly versatile solvents. If the high-boiling point aliphatic alcohol remains in the insulating layer, the semiconductor performance is deteriorated, and therefore, a low-boiling point lower aliphatic alcohol is suitable as the solvent.
  • Known resins that dissolve in lower aliphatic alcohols include butyral resin, polyvinyl alcohol, and alkyl methacrylate having a specific structure. However, butyral resin and polyvinyl alcohol have a hydroxyl group, and this hydroxyl group traps electric charge and deteriorates semiconductor performance.
  • Non-patent Document 1 Poly (n-butyl methacrylate) and poly (n-octyl methacrylate) are dissolved in lower aliphatic alcohols (Non-patent Document 1), and have no hydroxyl groups, so that they are used as insulating layer materials. When this occurs, the problem of charge trapping is less likely to occur.
  • these polymers do not have photocrosslinkability and, when used as an insulating layer, do not exhibit solvent resistance to organic solvents, making it difficult to form contact holes.
  • a polymer that can be dissolved in a lower aliphatic alcohol and that can be crosslinked (cured) is required as a polymer for forming the C layer.
  • a method using heat or radiation is generally used as the polymer crosslinking method.
  • the cross-linking by heating is not preferable from the viewpoint of suppressing performance degradation due to thermal expansion / contraction of the organic semiconductor layer as much as possible.
  • crosslinking by radiation is preferable, and crosslinking by ultraviolet rays (photocrosslinking) is particularly suitable.
  • the photocrosslinkable polymer can be obtained by introducing a photocrosslinkable functional group into the main chain or side chain of the polymer.
  • Various photo-crosslinkable functional groups are known, and polycyclic aromatic compounds such as anthracene and tetracene, coumarin (for example, Non-Patent Document 2) are known as those having high chemical stability to radicals.
  • Non-Patent Documents 3 and 4 are known as those having high chemical stability to radicals.
  • quinolinone for example, Non-Patent Documents 3 and 4
  • a photocrosslinkable polymer can be obtained by radical copolymerizing a monomer having these functional groups with another monomer.
  • Non-patent document 5 a copolymer of 6- (anthracen-9-yl) hexyl methacrylate and fluoroalkyl methacrylate
  • Non-patent document 6 diblock copolymer comprising poly (2-ethylhexyl methacrylate) and poly (9-anthrylmethyl methacrylate)
  • Non-patent Document 7 a technique related to (Non-Patent Document 7) is disclosed.
  • Patent Document 1 As a polymer containing coumarin and quinolinone, for example, a polymer for a liquid crystal alignment film has been proposed (for example, Patent Document 1). However, this polymer has a problem that it does not dissolve in lower aliphatic alcohols.
  • an organic transistor device basically includes three electrodes (a source electrode, a drain electrode, and a gate electrode), an insulating layer, and an organic semiconductor layer.
  • a source electrode a drain electrode, and a gate electrode
  • an organic semiconductor layer an organic semiconductor layer.
  • all printing methods for producing organic transistors by printing on plastics such as polyethylene naphthalate film.
  • the order in which the electrode, the insulating layer, and the organic semiconductor layer are formed differs depending on the form of the organic transistor. For example, by printing an aqueous or non-aqueous ink containing metal nanoparticles.
  • An electrode can be formed by printing a crosslinkable polymer solution, and an organic semiconductor layer can be formed by printing an organic semiconductor solution.
  • An organic solvent is used for the preparation of the polymer solution and the organic semiconductor solution.
  • PPX polyparaxylylene
  • BCB benzocyclobutene
  • PVP polyvinylphenol
  • FCE fluorine-based cyclic ether
  • the plastic of the base material is deformed by heating at the time of crosslinking, so that it is difficult to use other than engineering plastic films such as polyimide having excellent heat resistance.
  • the FCE polymer dissolves in a specific fluorine-based solvent such as perfluorotributylamine (PFTBA) but does not dissolve in a general-purpose organic solvent.
  • PFTBA perfluorotributylamine
  • the FCE polymer has a small surface tension, and when the organic semiconductor layer solution is printed on the polymer film, the solution does not spread and uniform printing is difficult. Further, the polymer and the solvent were both expensive and inferior in economic efficiency.
  • photocrosslinkable polymers that can be crosslinked at room temperature in a short time are attracting attention.
  • a polymer having a photocrosslinkable cinnamoyl group introduced into a polymer having a hydroxyl group such as poly (hydroxyethyl methacrylate) (for example, see Patent Document 2) and a polymer having a phenol group in the side chain have photocrosslinkability.
  • a polymer into which coumarin is introduced (for example, see Patent Document 3) has been proposed.
  • Patent Document 3 discloses a technique for reducing the amount of residual hydroxyl group by reacting an unreacted hydroxyl group with trifluoroacetic anhydride.
  • organic transistors are being developed as electronic devices.
  • This organic transistor is manufactured through a number of processes, and includes a process of forming an organic semiconductor film in a specific minute region.
  • This minute region is, for example, a rectangular region on the order of microns including a source electrode and a drain electrode.
  • an organic semiconductor solution is printed in the region using ink jet, it is necessary to drop the organic semiconductor solution in a minute region and prevent the organic semiconductor solution from getting wet out of the region.
  • a method for preventing wetting and spreading a method for preventing the solution from spreading out of the micro area by making only the above micro area lyophilic and making the outside of the area lyophobic is known. Yes.
  • the film is called a partition wall.
  • a fluorine-based resin having a low surface tension that exhibits liquid repellency to water and organic solvents is suitable.
  • a fluorine-based resin that is soluble in a solvent is required.
  • the fluorine-based resin include perfluorobutenyl ether polymers (product name: Cytop, manufactured by Asahi Glass). Tetrafluoroethylene / perfluorodioxole copolymer (manufactured by Mitsui DuPont Fluorochemicals, trade name Teflon (registered trademark) AF) and the like are known.
  • a fluorine-based solvent such as fluoroalkylamine is used as the solvent.
  • the adhesion problem can be solved by forming the insulating film and the partition with the same material, there is a problem that the partition dissolves when the insulating film is laminated.
  • dissolution of the partition wall greatly reduces the transistor performance due to peeling of the organic semiconductor film due to the flow of the partition wall or loss of uniformity of the insulating film thickness.
  • the material for forming the partition walls is required to be capable of being easily printed by being dissolved in a fluorinated solvent, and to be insoluble in the fluorinated solvent when forming the partition walls.
  • a resin crosslinking technique is known as such an insolubilization technique, and photocrosslinking is known as a technique capable of crosslinking in a short time.
  • a technique of a polyfluoroalkyl methacrylate copolymer having an azide group introduced has been proposed (see, for example, Patent Document 7).
  • the photocrosslinking rate is low, so that an ultraviolet irradiation amount of 1 J / cm 2 or more is necessary, and the productivity is low.
  • the surface tension was as high as 18 to 23 mN / m, and the liquid repellency was insufficient.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a polymer for forming an insulating layer which can be dissolved in a lower aliphatic alcohol and photocrosslinked in a short time with ultraviolet rays to form a contact hole. There is to do.
  • Another object of the present invention is to provide a polymer excellent in insulation that dissolves in a general-purpose solvent that can be used as an insulating layer of an organic transistor device and crosslinks at room temperature in a short time.
  • Another object is to provide a polymer that is soluble in a solvent, insolubilized in a solvent by photocrosslinking at room temperature in a short time, and exhibits liquid repellency.
  • R 1 represents either hydrogen or a C1-C6 alkyl group
  • L represents a divalent linking group having 1 to 14 carbon atoms
  • n represents 0 or 1
  • A, R 2 and R 3 is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl
  • X represents O or S
  • Q 1 and Q 2 are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1
  • G 1 , G 2 , R 4 to R 7 are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group, X 1 ⁇ X 4 each independently are O or S, r and s are each independently an integer of 0 to 3 Represent.) [3
  • R 1 represents either hydrogen or a C1-C6 alkyl group
  • L represents a divalent linking group having 1 to 14 carbon atoms
  • n represents 0 or 1
  • A, R 2 and R 3 is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl Consists of ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group (One of the groups, X represents O or S, and m represents an integer of 0 to
  • R 1 represents either hydrogen or a C1-C6 alkyl group
  • L represents a divalent linking group having 1 to 14 carbon atoms
  • n represents 0 or 1
  • A, R 2 and R 3 is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl Consists of ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group (One of the groups, X represents O or S, and m represents an integer of 0
  • Q 1 and Q 2 are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1
  • G 1 , G 2 , R 4 to R 7 are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group the one of the group consisting of, X 1 ⁇ X 4 are each independently O or S, And s
  • R 8 represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.
  • R 9 is either hydrogen or a C1-C6 alkyl group
  • M is a divalent linking group having 1 to 14 carbon atoms
  • k is 0 or 1
  • Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group
  • j is 0
  • R 10 represents hydrogen or a C1-C6 alkyl group
  • E represents —O—, —S—, or —NH—
  • t represents 0 or 1
  • R 11 represents 1 to Represents 18 fluoroalkyl groups.
  • R 8 represents either hydrogen or a C1-C6 alkyl group
  • Z represents a C1-C12 alkyl group.
  • R 9 is either hydrogen or a C1-C6 alkyl group
  • M is a divalent linking group having 1 to 14 carbon atoms
  • k is 0 or 1
  • Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group
  • j is 0
  • R 10 is hydrogen or a C1-C6 alkyl group
  • E is —O—, —S—, or —NH—
  • t is 0 or 1
  • R 11 is a fluoro having 1 to 18 carbon atoms. Represents an alkyl group.
  • [7] A crosslinked product of the polymer according to [3] to [6].
  • An insulating film containing at least one of the polymer according to [3] to [6] or the crosslinked product according to [7].
  • a protective film comprising at least one of the polymer according to [4] or the crosslinked product according to [7].
  • a liquid repellent film containing at least one of the polymer according to [6] or the crosslinked product according to [7].
  • An organic transistor device comprising the insulating film according to [8].
  • [12] An organic transistor device comprising the protective film according to [9].
  • the present invention is a polymerizable compound represented by the formula (1).
  • R 1 represents either hydrogen or a C1-C6 alkyl group
  • L represents a divalent linking group having 1 to 14 carbon atoms
  • n represents 0 or 1
  • A, R 2 and R 3 is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl One of the group consisting of ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group
  • X represents O or S
  • m represents an integer of 0 to 3.
  • the C1-C6 alkyl group for R 1 in the formula (1) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • L represents a divalent linking group having 1 to 14 carbon atoms.
  • the divalent linking group having 1 to 14 carbon atoms is not particularly limited as long as it is a divalent organic group that does not easily undergo structural change by radiation.
  • n 0 or 1.
  • A, R 2 and R 3 are each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl Ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkoxy group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl group, fluorothio group, cycloalkyl group, 1 type of the group which consists of a cycloheteroalkyl group is represented.
  • the halogen in A, R 2 and R 3 is not particularly limited, and examples thereof include chlorine and fluorine.
  • the C1-C18 alkyl group in A, R 2 and R 3 is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. It is done.
  • the alkoxy group in A, R 2 and R 3 is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, An isobutoxy group etc. are mentioned.
  • the alkylthio group in A, R 2 and R 3 is not particularly limited, and examples thereof include methylsulfanyl group, ethylsulfanyl group, isopropylsulfanyl group, n-propylsulfanyl group, n-butylsulfanyl group, isobutyl Examples thereof include a sulfanyl group and a sec-butylsulfanyl group.
  • the alkylamino group in A, R 2 and R 3 is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, a dimethylamino group, Examples thereof include a diethylamino group, a di (n-propyl) amino group, a methylethylamino group, and a methyl-n-propylamino group.
  • the alkyl ketone group in A, R 2 and R 3 is not particularly limited, and examples thereof include a methyl ketone group, an ethyl ketone group, an isopropyl ketone group, an n-propyl ketone group, an n-butyl ketone group, and an isobutyl ketone group. And sec-butyl ketone group.
  • the alkyl ester group in A, R 2 and R 3 is not particularly limited, and examples thereof include a methyl ester group, an ethyl ester group, an isopropyl ester group, an n-propyl ester group, an n-butyl ester group, Examples thereof include isobutyl ester group and sec-butyl ester group.
  • the alkylamide group in A, R 2 and R 3 is not particularly limited, and examples thereof include a methylamide group, an ethylamide group, an isopropylamide group, an n-propylamide group, an n-butylamide group, and an isobutylamide group. And sec-butylamide group.
  • the aryl group in A, R 2 and R 3 is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • the aryl ether group in A, R 2 and R 3 is not particularly limited, and examples thereof include a phenyl ether group, a naphthyl ether group, an anthryl ether group, and a biphenyl ether group.
  • the arylthio group in A, R 2 and R 3 is not particularly limited, and examples thereof include a phenylsulfanyl group, a naphthylsulfanyl group, an anthrylsulfanyl group, and a biphenylsulfanyl group.
  • the carboxyalkyl group in A, R 2 and R 3 is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, and a carboxy-n-butyl group. It is done.
  • the fluoroalkyl group in A, R 2 and R 3 is not particularly limited, and examples thereof include perfluoromethyl group, perfluoropropyl group, perfluorobutyl group, 1H, 1H-pentafluoropropyl group, 1H, 1H. , 2H, 2H-pentafluorobutyl group, 1H, 1H-heptafluorobutyl group, 4,4,4-trifluorobutyl group and the like.
  • the fluoroalkoxy group in A, R 2 and R 3 is not particularly limited, and examples thereof include perfluoromethoxy group, perfluoropropoxy group, perfluorobutoxy group, 1H, 1H-pentafluoropropoxy group, 1H, 1H. , 2H, 2H-pentafluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group, and the like.
  • the fluoroalkylcarbonyl group in A, R 2 and R 3 is not particularly limited, and examples thereof include a perfluoromethylcarbonyl group, a perfluoropropylcarbonyl group, a perfluorobutylcarbonyl group, and 1H, 1H-pentafluoropropylcarbonyl.
  • the fluoroalkyl ester group in A, R 2 and R 3 is not particularly limited, and examples thereof include a perfluoromethyl ester group, a perfluoropropyl ester group, a perfluorobutyl ester group, and a 1H, 1H-pentafluoropropyl ester.
  • a perfluoromethyl ester group a perfluoropropyl ester group
  • a perfluorobutyl ester group a 1H, 1H-pentafluoropropyl ester.
  • the fluoroaryl group in A, R 2 and R 3 is not particularly limited, and examples thereof include a 4-fluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 1-fluoro Examples include naphthyl group, octafluoronaphthyl group, 1-fluoroanthryl group, 2-fluoroanthryl group, 9-fluoroanthryl group, 2-fluorobiphenyl group, 4-fluorobiphenyl group, and the like.
  • the fluorothio group in A, R 2 and R 3 is not particularly limited, and examples thereof include perfluoromethylsulfanyl group, perfluoropropylsulfanyl group, perfluorobutylsulfanyl group, 1H, 1H-pentafluoropropylsulfanyl group, Examples thereof include 1H, 1H, 2H, 2H-pentafluorobutylsulfanyl group, 1H, 1H-heptafluorobutylsulfanyl group, 4,4,4-trifluorobutylsulfanyl group and the like.
  • the cycloalkyl group in A, R 2 and R 3 is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the cycloheteroalkyl group in A, R 2 and R 3 is not particularly limited, and examples thereof include 2-furyl group, 3-furyl group, tetrahydrothiophen-3-yl, and tetrahydrothiophen-2-yl.
  • 1-thiacyclohexane-4-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, tetrahydrothiophen-4-yl, tetrahydropyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-2- Ir etc. are mentioned.
  • X represents O or S.
  • m represents an integer of 0 to 3.
  • Another aspect of the present invention is a polymerizable compound represented by the following formula (2).
  • Q 1 and Q 2 are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1
  • G 1 , G 2 , R 4 to R 7 are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group and each X 1 ⁇ X 4 are independently O or S, r and s which Independently represents an integer of
  • Q 1 and Q 2 represent a divalent linking group having 1 to 14 carbon atoms.
  • the divalent linking group having 1 to 14 carbon atoms is not particularly limited as long as it is a divalent organic group that does not easily undergo structural change by radiation.
  • p and q each independently represent 0 or 1.
  • G 1 , G 2 and R 4 to R 7 are each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl Ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkoxy group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroaryl 1 type of the group which consists of group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group.
  • the halogen in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include chlorine, fluorine and the like.
  • the C1-C18 alkyl group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Groups and the like.
  • the alkoxy group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec -Butoxy group, isobutoxy group and the like.
  • the alkylthio group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a methylsulfanyl group, an ethylsulfanyl group, an isopropylsulfanyl group, an n-propylsulfanyl group, and n-butyl. Examples thereof include a sulfanyl group, an isobutylsulfanyl group, and a sec-butylsulfanyl group.
  • the alkylamino group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, Examples thereof include a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, a methylethylamino group, and a methyl-n-propylamino group.
  • the alkyl ketone group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a methyl ketone group, an ethyl ketone group, an isopropyl ketone group, an n-propyl ketone group, and an n-butyl ketone group. , Isobutyl ketone group, sec-butyl ketone group and the like.
  • the alkyl ester group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a methyl ester group, an ethyl ester group, an isopropyl ester group, an n-propyl ester group, an n- Examples thereof include a butyl ester group, an isobutyl ester group, a sec-butyl ester group and the like.
  • the alkylamide group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a methylamide group, an ethylamide group, an isopropylamide group, an n-propylamide group, and an n-butylamide group. , Isobutylamide group, sec-butylamide group and the like.
  • the aryl group in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • the aryl ether group in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include a phenyl ether group, a naphthyl ether group, an anthryl ether group, and a biphenyl ether group. .
  • the arylthio group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a phenylsulfanyl group, a naphthylsulfanyl group, an anthrylsulfanyl group, and a biphenylsulfanyl group.
  • the carboxyalkyl group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, and a carboxy-n-butyl group. Groups and the like.
  • the fluoroalkyl group in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include a perfluoromethyl group, a perfluoropropyl group, a perfluorobutyl group, and a 1H, 1H-pentafluoropropyl group. Examples thereof include 1H, 1H, 2H, 2H-pentafluorobutyl group, 1H, 1H-heptafluorobutyl group, 4,4,4-trifluorobutyl group and the like.
  • the fluoroalkoxy group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a perfluoromethoxy group, a perfluoropropoxy group, a perfluorobutoxy group, and a 1H, 1H-pentafluoropropoxy group.
  • 1H, 1H, 2H, 2H-pentafluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like can be mentioned.
  • the fluoroalkyl ether group in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include a perfluoromethoxy group, a perfluoropropoxy group, a perfluorobutoxy group, and 1H, 1H-pentafluoropropoxy group.
  • a perfluoromethoxy group a perfluoropropoxy group
  • a perfluorobutoxy group a perfluorobutoxy group
  • 1H, 1H-pentafluoropropoxy group 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like.
  • the fluoroalkylcarbonyl group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a perfluoromethylcarbonyl group, a perfluoropropylcarbonyl group, a perfluorobutylcarbonyl group, 1H, 1H— Examples thereof include a pentafluoropropylcarbonyl group, 1H, 1H, 2H, 2H-pentafluorobutylcarbonyl group, 1H, 1H-heptafluorobutylcarbonyl group, 4,4,4-trifluorobutylcarbonyl group and the like.
  • the fluoroalkyl ester group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a perfluoromethyl ester group, a perfluoropropyl ester group, a perfluorobutyl ester group, 1H, 1H— Examples thereof include a pentafluoropropyl ester group, 1H, 1H, 2H, 2H-pentafluorobutyl ester group, 1H, 1H-heptafluorobutyl ester group, 4,4,4-trifluorobutyl ester group and the like.
  • the fluoroaryl group in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include a 4-fluorophenyl group and a 2,3,4,5,6-pentafluorophenyl group.
  • the fluorothio group in G 1 , G 2 , R 4 to R 7 is not particularly limited, and examples thereof include a perfluoromethylsulfanyl group, a perfluoropropylsulfanyl group, a perfluorobutylsulfanyl group, and 1H, 1H-pentafluoro.
  • examples thereof include a propylsulfanyl group, 1H, 1H, 2H, 2H-pentafluorobutylsulfanyl group, 1H, 1H-heptafluorobutylsulfanyl group, 4,4,4-trifluorobutylsulfanyl group and the like.
  • the cycloalkyl group in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the cycloheteroalkyl group in G 1 , G 2 and R 4 to R 7 is not particularly limited, and examples thereof include 2-furyl group, 3-furyl group, tetrahydrothiophen-3-yl, tetrahydrothiophene.
  • X 1 to X 4 each independently represents O or S.
  • r and s each independently represent an integer of 0 to 3.
  • the present invention includes at least one of the following formulas (3) to (5) obtained by using the polymerizable compound represented by the above formula (1) or the above formula (2) as a repeating unit, And it is a polymer containing at least 1 type of repeating unit of the group which consists of the following formula
  • R 1 represents either hydrogen or a C1-C6 alkyl group
  • L represents a divalent linking group having 1 to 14 carbon atoms
  • n represents 0 or 1
  • A, R 2 and R 3 are each independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group , Aryl group, aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cyclo One of the group consisting of heteroalkyl groups, X represents O or S, and m represents an integer of 0 to 3.
  • Q 1 and Q 2 are each independently a divalent linking group having 1 to 14 carbon atoms, p and q are each independently 0 or 1
  • G 1 , G 2 , R 4 to R 7 are each independently hydrogen, halogen, cyano group, nitro group, C1 to C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group , Aryl ether group, arylthio group, carboxyalkyl group, fluoroalkyl group, fluoroalkyl ether group, fluoroalkylcarbonyl group, fluoroalkyl ester group, fluoroalkoxy group, fluoroaryl group, fluorothio group, cycloalkyl group, cycloheteroalkyl group the one of the group consisting of, X 1 ⁇ X 4 are each independently O or S, And s
  • R 8 represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.
  • R 9 is either hydrogen or a C1-C6 alkyl group
  • M is a divalent linking group having 1 to 14 carbon atoms
  • k is 0 or 1
  • Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group
  • j is 0
  • R 10 represents hydrogen or a C1-C6 alkyl group
  • E represents —O—, —S—, or —NH—
  • t represents 0 or 1
  • R 11 represents 1 to Represents 18 fluoroalkyl groups.
  • the present invention is preferably a polymer containing repeating units represented by the following formulas (4) and (6). Thereby, the polymer of this invention can be used more suitably as an insulating film or a protective film.
  • R 8 represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.
  • R 8 represents either hydrogen or a C1-C6 alkyl group, and Z represents a C1-C12 alkyl group.
  • R 8 represents hydrogen or a C1-C6 alkyl group.
  • the C1-C6 alkyl group in R 8 is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • Z represents a C1-C12 alkyl group.
  • the C1-C12 alkyl group in Z is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • the polymer of the present invention is preferably a polymer including at least one of the following formulas (3) to (5) as a repeating unit and including a repeating unit represented by the formula (7).
  • R 9 is either hydrogen or a C1-C6 alkyl group
  • M is a divalent linking group having 1 to 14 carbon atoms
  • k is 0 or 1
  • Y is hydrogen, halogen, Cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group, aryl group, aryl ether group, arylthio group, carboxyalkyl group, One of the group consisting of a fluoroalkyl group, a fluoroalkyl ether group, a fluoroalkylcarbonyl group, a fluoroalkyl ester group, a fluoroalkoxy group, a fluoroaryl group, a fluorothio group, a cycloalkyl group, and a cycloheteroalkyl group
  • j is 0
  • the polymer of the present invention preferably contains at least repeating units of the above formulas (3) and (7).
  • the polymer of the present invention preferably contains at least a repeating unit of the above formula (4).
  • the polymer of the present invention preferably contains a repeating unit of the above formula (7).
  • the polymer of the present invention includes a polymer containing the above formula (4) and the above formula (7) as repeating units, a polymer containing the above formula (5) and the above formula (7) as repeating units, and the above formula (4). It is preferably one of the group consisting of polymers containing the above formulas (5) and (7) as repeating units, and more preferably a polymer containing the above formulas (4) and (7) as repeating units. It is a coalescence. Thereby, it is possible to crosslink by irradiation with short radiation, and the insulation performance of the obtained crosslinked body is improved.
  • the ratio of the repeating units of the above formulas (4), (5) and (7) is not particularly limited, and can be appropriately determined depending on the balance between solubility in an organic solvent and crosslinkability by ultraviolet rays.
  • the ratio of is 40 mol% or more.
  • R 9 represents hydrogen or a C1-C6 alkyl group.
  • the C1-C6 alkyl group for R 9 in formula (7) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • M is not particularly limited as a divalent linking group having 1 to 14 carbon atoms.
  • —C (O) O—, —OC (O) —, —C (O) OCH 2 —, —CH 2 —, —C (O) —, —O—, —OCH 2 CH 2 O— and the like can be mentioned.
  • k 0 or 1.
  • each Y is independently hydrogen, halogen, cyano group, nitro group, C1-C18 alkyl group, alkoxy group, alkylthio group, alkylamino group, alkyl ketone group, alkyl ester group, alkylamide group.
  • the halogen in Y is not particularly limited, and examples thereof include chlorine and fluorine.
  • the C1-C18 alkyl group in Y is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • the alkoxy group in Y is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and an isobutoxy group. .
  • the alkylthioether group in Y is not particularly limited, and examples thereof include methylsulfanyl group, ethylsulfanyl group, isopropylsulfanyl group, n-propylsulfanyl group, n-butylsulfanyl group, isobutylsulfanyl group, sec- A butylsulfanyl group etc. are mentioned.
  • the alkylamino group in Y is not particularly limited, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, a dimethylamino group, a diethylamino group, a di (n -Propyl) amino group, methylethylamino group, methyl-n-propylamino group and the like.
  • the alkyl ketone group in Y is not particularly limited, and examples thereof include a methyl ketone group, an ethyl ketone group, an isopropyl ketone group, an n-propyl ketone group, an n-butyl ketone group, an isobutyl ketone group, and a sec-butyl ketone group. Is mentioned.
  • the alkyl ester group in Y is not particularly limited.
  • methyl ester group, ethyl ester group, isopropyl ester group, n-propyl ester group, n-butyl ester group, isobutyl ester group, sec- A butyl ester group etc. are mentioned.
  • the alkylamide group in Y is not particularly limited, and examples thereof include a methylamide group, an ethylamide group, an isopropylamide group, an n-propylamide group, an n-butylamide group, an isobutylamide group, and a sec-butylamide group. Is mentioned.
  • the aryl group in Y is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • the aryl ether group in Y is not particularly limited, and examples thereof include a phenyl ether group, a naphthyl ether group, an anthryl ether group, and a biphenyl ether group.
  • the arylthioether group in Y is not particularly limited, and examples thereof include a phenylsulfanyl group, a naphthylsulfanyl group, an anthrylsulfanyl group, and a biphenylsulfanyl group.
  • the carboxyalkyl group in Y is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, and a carboxy-n-butyl group.
  • the fluoroalkyl group in Y is not particularly limited, and examples thereof include perfluoromethyl group, perfluoropropyl group, perfluorobutyl group, 1H, 1H-pentafluoropropyl group, 1H, 1H, 2H, 2H-penta.
  • a fluorobutyl group, 1H, 1H-heptafluorobutyl group, 4,4,4-trifluorobutyl group and the like can be mentioned.
  • the fluoroalkoxy group in Y is not particularly limited, and examples thereof include perfluoromethoxy group, perfluoropropoxy group, perfluorobutoxy group, 1H, 1H-pentafluoropropoxy group, 1H, 1H, 2H, 2H-penta. Examples thereof include a fluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like.
  • the fluoroalkyl ether group in Y is not particularly limited, and examples thereof include perfluoromethoxy group, perfluoropropoxy group, perfluorobutoxy group, 1H, 1H-pentafluoropropoxy group, 1H, 1H, 2H, 2H— A pentafluorobutoxy group, 1H, 1H-heptafluorobutoxy group, 4,4,4-trifluorobutoxy group and the like can be mentioned.
  • the fluoroalkylcarbonyl group in Y is not particularly limited, and examples thereof include a perfluoromethylcarbonyl group, a perfluoropropylcarbonyl group, a perfluorobutylcarbonyl group, a 1H, 1H-pentafluoropropylcarbonyl group, 1H, 1H, Examples include 2H, 2H-pentafluorobutylcarbonyl group, 1H, 1H-heptafluorobutylcarbonyl group, 4,4,4-trifluorobutylcarbonyl group, and the like.
  • the fluoroalkyl ester group in Y is not particularly limited, and examples thereof include perfluoromethyl ester group, perfluoropropyl ester group, perfluorobutyl ester group, 1H, 1H-pentafluoropropyl ester group, 1H, 1H, Examples include 2H, 2H-pentafluorobutyl ester group, 1H, 1H-heptafluorobutyl ester group, 4,4,4-trifluorobutyl ester group and the like.
  • the fluoroaryl group in Y is not particularly limited, and examples thereof include 4-fluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 1-fluoronaphthyl group, and octafluoronaphthyl.
  • 4-fluorophenyl group 2,3,4,5,6-pentafluorophenyl group, 1-fluoronaphthyl group, and octafluoronaphthyl.
  • the fluorothioether group in Y is not particularly limited, and examples thereof include perfluoromethylsulfanyl group, perfluoropropylsulfanyl group, perfluorobutylsulfanyl group, 1H, 1H-pentafluoropropylsulfanyl group, 1H, 1H, 2H. , 2H-pentafluorobutylsulfanyl group, 1H, 1H-heptafluorobutylsulfanyl group, 4,4,4-trifluorobutylsulfanyl group and the like.
  • the cycloalkyl group in Y is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the cycloheteroalkyl group in Y is not particularly limited, and examples thereof include 2-furyl group, 3-furyl group, tetrahydrothiophen-3-yl, tetrahydrothiophen-2-yl, 1-thiacyclohexane- Examples include 4-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, tetrahydrothiophen-4-yl, tetrahydropyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-2-yl and the like.
  • j represents an integer of 0 to 5.
  • the polymer of the present invention preferably contains a repeating unit represented by the following formula (4) and the following formula (8).
  • R 10 is hydrogen or a C1-C6 alkyl group
  • E is —O—, —S—, or —NH—
  • t is 0 or 1
  • R 11 is a fluoro having 1 to 18 carbon atoms. Represents an alkyl group.
  • R 10 represents hydrogen or a C1-C6 alkyl group.
  • the C1-C6 alkyl group for R 10 in formula (8) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • E represents —O—, —S—, or —NH—.
  • k 0 or 1.
  • R 11 represents a fluoroalkyl group having 1 to 18 carbon atoms.
  • the fluoroalkyl group for R 11 is not particularly limited, and examples thereof include 2,2,2-trifluoroethyl group, 1,1,1,2,2-pentafluoropropyl group, 1,1 1,1,2,2-pentafluorobutyl group, 1,1,1,2,2-pentafluoropentyl group, 1,1,1,2,2,3,3-heptafluorohexyl group, 1,1, Examples include 1,2,2,3,3-heptafluoroheptyl group, 1,1,1,2,2,3,3-heptafluorooctyl group, hexafluoroisobutyl group and the like.
  • the polymerizable compound represented by the formulas (1) and (2) of the present invention has a benzopyran group that is a photocrosslinkable functional group. Therefore, a copolymer (polymer) obtained by copolymerizing the polymerizable compound with another polymerizable compound has photocrosslinkability, and the photocrosslinkability depends on the amount of the polymerizable compound introduced. It changes depending on.
  • the polymerizable compound represented by the formula (1) of the present invention has a feature that the influence on the solubility in a lower alcohol is small. When the polymerizable compound according to the present invention is used, A copolymer (polymer) excellent in both solubility in a lower alcohol can be obtained.
  • the polymerizable compound represented by the formulas (1) and (2) of the present invention is suitably used as a polymer obtained by polymerization using the polymerizable compound as a monomer.
  • the polymerizable compound represented by the formula (1) is a repeating unit represented by the formula (4)
  • the polymerizable compound represented by the formula (2) is represented by the formula (5). It becomes a repeating unit represented by.
  • the repeating unit represented by the formula (4) is a photocrosslinking group, and the content thereof is shortening of the photocrosslinking time, high crosslink density (excellent solvent resistance), and dissolution in a lower aliphatic alcohol. From the viewpoint of properties, when the total of repeating units of formulas (6) and (4) is 100 mol%, the ratio of the repeating units represented by formula (4) is preferably 5 to 35 mol%. .
  • M is the number of the longest carbon chains constituting L in the formula (4), it is more preferable to complete photocrosslinking in a short time. Therefore, this M constitutes Z in the formula ((6)) It is preferable that N + 2 ⁇ M ⁇ N ⁇ 2 is satisfied with respect to the number N of the longest carbon chains.
  • the polymer containing at least one of the above formula (4) and formula (5) as a repeating unit and containing a repeating unit represented by formula (7) is crosslinked.
  • the polymer which performed can be shown.
  • Radiation is preferably used for the crosslinking treatment.
  • Examples of radiation include ultraviolet rays having a wavelength of 245 to 350 nm.
  • the amount of radiation irradiation is appropriately changed depending on the composition of the polymer, and examples thereof include 100 to 500 mJ / cm 2 , and further 100 to 300 mJ / cm 2, which prevents a reduction in the degree of crosslinking and shortens the process. In order to improve the economic efficiency due to time, it is preferably 50 to 300 mJ / cm 2 and 50 to 200 mJ / cm 2 .
  • the environment in particular when irradiating an ultraviolet-ray is not restrict
  • Whether the copolymer is cross-linked can be determined by the solubility when the copolymer film is immersed in a good solvent, and the degree of cross-linking can be quantitatively evaluated by measuring the residual film rate described later. Specifically, if the copolymer thin film formed on the glass plate is immersed in a good solvent without being crosslinked, the copolymer film is completely dissolved. On the other hand, a sufficiently crosslinked copolymer film does not dissolve in a good solvent, maintains a solid state, and does not change the thickness of the film. In addition, when the crosslinking is insufficient, the polymer film maintains a solid state, but a part of the copolymer is dissolved, so that the film thickness becomes small.
  • the structure of the polymer after the crosslinking treatment can be identified by a method using a thermogravimetric / mass spectrometer (TG-MS) and an infrared absorption spectrum (IR).
  • TG-MS thermogravimetric / mass spectrometer
  • IR infrared absorption spectrum
  • the molecular weight of the polymer containing at least one repeating unit of the group consisting of the above formulas (3) to (8) for example, 5000 to 1,000,000 (g / mol).
  • Etc From the viewpoint of the solution viscosity of the polymer and the mechanical strength, it is preferably 10,000 to 500,000 (g / mol).
  • the polymer of the present invention can be obtained by polymerizing the monomers represented by the above formulas (1) and (9) by a known radical polymerization method.
  • the polymer of the present invention can be obtained by polymerizing at least one monomer of the formula (1) or the formula (2) and a monomer represented by the formula (10) by a radical polymerization method. it can.
  • R 9 , M, Y, k and j are the same as those defined in the formula (7)).
  • the polymer of the present invention can be obtained by polymerizing the monomers represented by the above formulas (1) and (11) by a known radical polymerization method.
  • R 10 , R 11 , E, and t are the same as those defined in formula (8).
  • specific examples of the polymerizable compound represented by the formula (1) include the following in addition to 7-methacryloyloxy-4-oxobenzopyran represented by the formula (12). It is done.
  • At least one monomer of the group consisting of the monomer represented by [Chemical Formula 33] and the monomer represented by [Chemical Formula 36 to Chemical Formula 56] is polymerized. It is preferable. As a result, it is dissolved in a lower aliphatic alcohol, photocrosslinked in a short time with ultraviolet rays, and becomes a polymer for forming an insulating layer capable of forming a contact hole.
  • the polymerizable compound represented by the formula (1) of the present invention can be produced by a known method in which a benzopyran compound having a hydroxy group and an acid chloride are reacted in a solvent.
  • a benzopyran compound having a hydroxy group and an acid chloride are reacted in a solvent.
  • the acid chloride acryloyl chloride, methacryloyl chloride, 2-alkyl acryloyl chloride, or 2-alkyl methacryloyl chloride is used, and the molar ratio of acid chloride to the benzopyran compound is reduced to reduce the amount of unreacted acid chloride. .5 to 1.0 is preferable.
  • Solvents that can be used in this reaction dissolve the above-mentioned benzopyran compound and acid chloride, do not react with these compounds, and are not limited as long as they are sufficiently dehydrated.
  • tetrahydrofuran methylene chloride, toluene, etc.
  • an acid acceptor for hydrogen chloride generated in the reaction and an esterification catalyst, and a polymerization inhibitor for preventing polymerization of a polymerizable compound during the reaction Is preferably added.
  • the acid acceptor include dehydrated triethylamine and pyridine
  • examples of the catalyst include strong bases such as N, N-dimethyl-4-aminopyridine
  • examples of the polymerization inhibitor include hydroquinone and dibutylhydroxytoluene.
  • the reaction temperature is not particularly limited, but is preferably 0 to 60 ° C. in order to prevent polymerization reaction.
  • the reaction time is not particularly limited, but is preferably 2 to 6 hours because of excellent economic efficiency.
  • the polymerizable compound represented by the formula (1) of the present invention can also be produced using a known method.
  • 6-vinyl-4-oxo-benzopyran compound, or 7-vinyl-4-oxo-benzopyran compound starts from 6-methyl-4-oxo-benzopyran compound, or 7-methyl-4-oxo-benzopyran compound Raw material, a step of bromomethylating a methyl group using a carbon tetrachloride as a solvent and a radical generator such as N-bromosuccinimide, a peroxide compound, or azoisobutyronitrile, a bromomethyl group as a solvent and a dimethylsulfoxide as a solvent
  • the catalyst can be used for the formylation with sodium hydrogencarbonate, and the formyl group can be produced by four processes for vinylation with potassium tert-butoxide using methyltriphenylphosphonium bromide as a catalyst.
  • the polymerizable compound represented by the formula (2) of the present invention can be produced by a known method in which a benzopyran compound having a hydroxy group and an acid chloride are reacted in a solvent.
  • the acid chloride include acid chlorides such as fumaric acid dichloride and maleic acid dichloride.
  • the molar ratio of the acid chloride to the benzopyran compound is preferably 0.35 to 0.45 in order to reduce the amount of unreacted acid chloride.
  • the solvent that can be used in this reaction is not limited as long as it dissolves the above-mentioned benzopyran compound and acid chloride, does not react with these compounds, and is sufficiently dehydrated.
  • N, N-dimethylacetamide An amide solvent such as N-methylpyrrolidone can be used.
  • an acid acceptor for hydrogen chloride generated in the reaction and an esterification catalyst, and a polymerization inhibitor for preventing polymerization of a polymerizable compound during the reaction Is preferably added.
  • the acid acceptor include dehydrated triethylamine and pyridine
  • examples of the catalyst include strong bases such as N, N-dimethyl-4-aminopyridine
  • examples of the polymerization inhibitor include hydroquinone and dibutylhydroxytoluene.
  • the reaction temperature is not particularly limited, but is preferably 0 to 70 ° C. in order to prevent the polymerization reaction.
  • the reaction time is not particularly limited, but is preferably 2 to 6 hours because of excellent economic efficiency.
  • specific examples of the monomer represented by the formula (10) include styrene, ⁇ -methylstyrene, 2-chlorostyrene, 2-bromostyrene, 2-fluorostyrene, 3-chlorostyrene, 3-bromostyrene, 3-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-fluorostyrene, 4-chloromethylstyrene, 3,5-trifluoromethylstyrene, 4-trifluorostyrene, 2,3, 4,5,6-pentafluorostyrene may be mentioned.
  • specific monomers represented by the formula (11) include, in addition to 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate represented by the formula (13), for example, the following: Can be mentioned.
  • radical copolymerization When radically copolymerizing the monomer represented by the above formula (1) or (2) and the monomer represented by at least one selected from the group consisting of the formulas (9) to (11), for the radical copolymerization, known methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can be used.
  • the solvent used in the solution polymerization is not limited as long as the above-described monomer and the polymer of the present invention are dissolved.
  • amide solvents such as dimethylformamide and dimethylacetamide; toluene, xylene, 1,3-bis Aromatic hydrocarbon solvents such as (trifluoromethyl) benzene and ⁇ , ⁇ , ⁇ -trifluoromethylbenzene; cyclic ethers such as tetrahydrofuran and tetrahydropyran, and the like.
  • These solvents can also be used in combination.
  • the polymerization temperature is selected depending on the initiator used, but is not particularly limited.
  • any of azo initiators such as azoisobutyronitrile; peroxide initiators such as benzoyl peroxide and di (t-butyl) peroxide can be used.
  • the reaction time is set according to the half-life of the initiator used and is not limited at all, but is preferably 4 to 8 hours from the viewpoint of economy.
  • the polymer of the present invention can be applied or printed on various substrates in a solution state dissolved in a solvent.
  • the solvent can be used without any limitation as long as it dissolves the polymer and at the same time does not dissolve the organic semiconductor used in the production of the organic transistor.
  • aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, t-butanol, n-pentanol and the like can be applied on the organic semiconductor layer.
  • aliphatic alcohols having 4 or less carbon atoms are more preferred.
  • coating or printing method there are no restrictions on the coating or printing method, such as spin coating, drop casting, dip coating, doctor blade coating, pad printing, squeegee coating, roll coating, rod bar coating, air knife coating, wire bar coating, flow coating, Printing can be performed using gravure printing, flexographic printing, screen printing, inkjet printing, letterpress reverse printing, and the like.
  • this insulating layer needs the solubility with respect to said solvent.
  • a fluorine-containing monomer represented by the formula (10) and having a specific structure such as 2,3,4,5,6-pentafluorostyrene is used, the polymer of the present invention is soluble in a general-purpose solvent. However, it also dissolves in fluorinated solvents.
  • the polymer of the present invention is dissolved in a fluorine-based solvent such as hexafluorobenzene, 2,3,4,5,6-pentafluorotoluene and printed on the uppermost layer of the organic transistor element as a protective film.
  • a fluorine-based solvent such as hexafluorobenzene, 2,3,4,5,6-pentafluorotoluene
  • the polymer according to the present invention has a photocrosslinkable group, and radiation is suitably used for the photocrosslinking (photocyclization).
  • the radiation include ultraviolet rays having a wavelength of 245 to 350 nm.
  • the irradiation amount of radiation is appropriately changed depending on the composition of the polymer. For example, it is 100 to 500 mJ / cm 2, and it is possible to prevent a decrease in the degree of crosslinking and improve economy by shortening the process. It is preferably 50 to 300 mJ / cm 2 .
  • Irradiation with ultraviolet rays is usually carried out in the atmosphere, but it can also be carried out in an inert gas or in a certain amount of inert gas flow as necessary.
  • a photosensitizer can be added to promote the photocrosslinking reaction.
  • the photosensitizer used is not particularly limited, and examples thereof include benzophenone compounds, anthraquinone compounds, thioxanthone compounds, nitrophenyl compounds, and the like, and benzophenone compounds having high compatibility with the polymer used in the present invention are preferable.
  • the sensitizers can be used in combination of two or more as required.
  • the polymer of the present invention can be photocrosslinked by ultraviolet rays, but may be heated if necessary.
  • the temperature in the case of heating in addition to ultraviolet irradiation is not particularly limited, a temperature of 120 ° C. or lower is preferable in order to avoid thermal deformation of the polymer used.
  • the polymer of the present invention contains a compound containing a plurality of olefins such as ethylene and propylene as a crosslinking agent in one molecule as a crosslinking agent in order to increase the crosslinking density or shorten the crosslinking time;
  • a compound containing a plurality of cyclic olefins such as cyclopentene in one molecule may be blended. These compounds may be used alone or in combination of two or more.
  • the polymer of the present invention can be efficiently photocrosslinked in a short time, and in order to efficiently photocrosslink in a shorter time, the time required for photocrosslinking is preferably within 2 minutes. In addition, since it is suitable for control of crosslinking time, it is more preferable that the time required for crosslinking is within 1 minute.
  • specific examples of the monomer represented by the formula (1) include the following in addition to 6- (chromone-7-oxy) hexamethyl methacrylate represented by the formula (14). It is done.
  • the polymer of the present invention can be suitably used as an insulating film containing the polymer of the present invention and / or a crosslinked product of the polymer of the present invention.
  • the polymer of the present invention can be suitably used as an organic transistor device including the insulating film.
  • the polymer of the present invention can be suitably used as a protective film containing the polymer of the present invention and / or a crosslinked product of the polymer of the present invention. Moreover, the polymer of this invention can be used suitably as an organic transistor device containing this protective film.
  • the polymer of the present invention can be suitably used as a liquid repellent film (layer) containing the polymer of the present invention and / or a crosslinked product of the polymer of the present invention.
  • the polymer of the present invention can be suitably used as an electronic device including the liquid repellent film, particularly as an organic transistor device.
  • the organic transistor of the present invention When the polymer of the present invention is used in an organic transistor device (hereinafter referred to as “organic transistor”), the organic transistor of the present invention has a bottom gate-top contact type (A), bottom gate-bottom contact type (A) shown in FIG. B), top gate-top contact type (C), and top gate-bottom contact type (D) may be used.
  • the polymer of the present invention has particularly high applicability to devices in the forms of (C) and (D).
  • 1 is an organic semiconductor layer
  • 2 is a substrate
  • 3 is a gate electrode
  • 4 is a gate insulating layer
  • 5 is a source electrode
  • 6 is a drain electrode.
  • the polymer of the present invention when used as a protective layer (film) for the organic semiconductor layer, the polymer can be used in either an uncrosslinked state or a crosslinked state.
  • a substrate that can be used is not particularly limited as long as sufficient flatness capable of producing an element can be ensured.
  • Plastics used as the substrate include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene / vinyl acetate copolymer, polymethylpentene-1, and polypropylene.
  • the organic semiconductor that can be used in the present invention is not limited at all, and any of N-type and P-type organic semiconductors can be used, and it can also be used as a bipolar transistor that combines N-type and P-type. Moreover, both low molecular and high molecular organic semiconductors can be used, and these can also be mixed and used. Specific examples of the compound include formulas (F-1) to (F-11).
  • examples of the method for forming the organic semiconductor layer include a method in which the organic semiconductor is vacuum-deposited, a method in which the organic semiconductor is dissolved in an organic solvent, and a method for coating and printing.
  • concentration of the solution when the organic semiconductor layer is applied or printed using a solution in which the organic semiconductor layer is dissolved in an organic solvent varies depending on the structure of the organic semiconductor and the solvent to be used, but the viewpoint of forming a more uniform semiconductor layer and reducing the thickness of the layer Therefore, it is preferably 0.5 to 5% by weight.
  • the organic solvent at this time is not limited as long as the organic semiconductor dissolves at a certain concentration capable of forming a film, and is hexane, heptane, octane, decane, dodecane, tetradecane, decalin, indane, 1-methylnaphthalene, 2-ethyl.
  • a solvent having a high solubility of an organic semiconductor and a boiling point of 100 ° C. or more is suitable, and xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole. Pentylbenzene, tetralin, cyclohexylbenzene, and decahydro-2-naphthol are preferred.
  • the mixed solvent which mixed 2 or more types of the above-mentioned solvent in the appropriate ratio can also be used.
  • the organic transistor of the present invention can be suitably used as an organic transistor having contact holes formed by etching.
  • the solvent used for etching at the time of contact hole formation is not limited as long as it is a solvent that dissolves the polymer of the present invention and the organic semiconductor to be used.
  • Examples include general-purpose aromatic hydrocarbon solvents such as benzene and 1,3-dimethoxybenzene. If the above conditions are satisfied, a mixed solvent in which two or more of these solvents are mixed can also be used.
  • organic / inorganic polymers or oligomers, or organic / inorganic nanoparticles can be added as solids or as dispersions in which nanoparticles are dispersed in water or an organic solvent.
  • a protective film can be formed by applying a polymer solution on the body layer. Furthermore, various moisture-proof coatings and light-resistant coatings can be applied on the protective film as necessary.
  • Examples of a gate electrode, a source electrode, or a drain electrode that can be used in the present invention include aluminum, gold, silver, copper, highly doped silicon, polysilicon, silicide, tin oxide, indium oxide, indium tin oxide, chromium, Examples include conductive materials such as inorganic electrodes such as platinum, titanium, tantalum, graphene, and carbon nanotubes, or organic electrodes such as doped conductive polymers (for example, PEDOT-PSS). It can also be used by laminating. Moreover, in order to raise the injection
  • the method for forming the electrode on the substrate, the insulating layer, or the organic semiconductor layer includes vapor deposition, high-frequency sputtering, electron beam sputtering, and the like.
  • Methods such as solution spin coating, drop casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, ink jet printing, letterpress reverse printing, etc., using ink dissolved in an organic solvent Can also be adopted.
  • the surface of the insulating layer is increased by irradiating the surface of the insulating layer with vacuum ultraviolet (VUV) light after UV crosslinking of the insulating layer and using a light shielding mask.
  • VUV vacuum ultraviolet
  • the irradiation time of VUV light varies depending on the structure of the polymer used in the insulating layer to be used and the distance between the light source and the surface of the insulating layer, but is preferably 1 minute to 8 minutes, more preferably 1 minute to 5 minutes from the viewpoint of economy. Minutes.
  • the mobility of the organic transistor of the present invention is preferably 0.20 cm 2 / Vs or more from the viewpoint of practicality of the organic transistor element.
  • the organic transistor of the present invention preferably has a threshold voltage of -10.0 V or higher and lower than 0 V from the viewpoint of practicality of the organic transistor element.
  • the organic transistor of the present invention preferably has a leakage current density of 10 ⁇ 9 A / cm 2 or less from the viewpoint of practicality of the organic transistor element.
  • a polymer for forming an insulating layer which can be dissolved in a lower aliphatic alcohol and photocrosslinked in a short time with ultraviolet rays to form a contact hole.
  • the present invention it is possible to provide a polymer that dissolves in a general-purpose solvent, crosslinks at room temperature in a short time, and has excellent insulating properties.
  • ADVANTAGE OF THE INVENTION According to this invention, the polymer which is soluble in a solvent, photocrosslinks in normal temperature for a short time, insolubilizes in a solvent, and shows liquid repellency can be provided.
  • FIG. 2 is a view showing a 1 H-NMR chart of a polymerizable compound produced in Example 1.
  • FIG. 2 is a diagram showing a 13 C-NMR chart of a polymerizable compound produced in Example 1.
  • FIG. 2 is a diagram showing a 1 H-NMR chart of a polymerizable compound produced in Example 2.
  • FIG. 2 is a diagram showing a 1 H-NMR chart of a polymerizable compound produced in Example 3.
  • FIG. 2 is a diagram showing a 1 H-NMR chart of a polymerizable compound produced in Example 4.
  • FIG. 3 is a view showing a 1 H-NMR chart of polymer 1 produced in Example 5.
  • FIG. 2 is a diagram showing a 1 H-NMR chart of polymer 6 produced in Example 10.
  • FIG. 2 is a view showing a 1 H-NMR chart of polymer 7 produced in Example 11.
  • FIG. 3 is a view showing a 1 H-NMR chart of polymer 8 produced in Example 12.
  • FIG. 2 is a view showing a 1 H-NMR chart of polymer 12 produced in Example 15.
  • the organic semiconductor (di-n-hexyldithienobenzodithiophene) used in the examples was synthesized according to the production method described in JP-A-2015-224238.
  • 7-Hydroxy-4-oxo-benzopyran (7HOB) was synthesized by the method described in Journal of Heterocyclic Chemistry, 2015, 52, 562 pages.
  • Kiesel-Gel-60 poly (n- butyl acrylate), polyvinyl butyral, and poly (vinyl alcohol) is with a reagent manufactured by Sigma-Aldrich.
  • Poly (n-octyl methacrylate) was synthesized according to the method described in Polymer Science, Series B, 2016, Vol. 58, No. 6, page 675.
  • a product Cytop manufactured by AGC Asahi Glass Co., Ltd. was used for the fluorine-based cyclic ether polymer, and perfluorotributylamine (CYTOP CT-SOLV180 manufactured by AGC Asahi Glass Co., Ltd.) was used as the solvent for Cytop.
  • 7-Methyl-4-oxo-benzopyran was prepared according to the method described in Journal of Heterocyclic Chemistry, Vol. 52, No. 2, 562, 2015. 7-formyl-4-oxo-benzopyran is described in Journal of Organic Chemistry, Vol. 58, No. 26, p. 598, 1993, by the method described in Medical Chemistry, Vol. 44, 672, 2001. 7-vinyl-4-oxo-benzopyran was prepared by the method described in Journal of American Chemical Society, Vol. 126, No. 12, p. 3856, 2004.
  • NMR NMR
  • polymer solubility polymer solubility
  • filterability spin coating
  • film thickness measurement UV irradiation
  • vacuum deposition residual film rate
  • contact angle surface tension
  • dielectric breakdown strength dispenser printing
  • partition wall formation The evaluation of the organic transistor element was carried out under the following conditions / apparatus.
  • ⁇ NMR> JNM-ECZ400S FT-NMR manufactured by JEOL Ltd. was used for measurement using a polymer deuterated chloroform solvent.
  • X a (I 1 + I 2 ) / ⁇ a (I 1 + I 2 ) + bI 3 ⁇ (Where I 1 represents the peak intensity at ⁇ 8.0 to 8.3 ppm, I 2 represents the peak intensity at ⁇ 6.0 to 6.5 ppm, and I 3 represents the peak intensity at ⁇ 3.3 to 4.1 ppm, a represents the number of hydrogen atoms bonded to the carbon adjacent to the ester group in the substituent Z of the formula (6), and b represents the total number of hydrogen atoms of the substituents R 2 and R 3 of the benzopyran group in the formula (4).
  • the benzopyran group content X was calculated by the following method using 1 H-NMR according to the following formula.
  • X (3I 2 ⁇ aI 1 ) / ⁇ (5-a) I1 + 2I 2 ⁇ (Where I 1 is the peak intensity at ⁇ 0.8 to 2.5 ppm, I 2 is the peak intensity at ⁇ 6.0 to 8.5 ppm, and a is bonded to the phenyl group in formula (4) or (5).
  • the content X of the chromone group was calculated by the following formula using 1 H-NMR.
  • ⁇ Vacuum deposition> A small vacuum deposition apparatus VTR-350M / ERH manufactured by ULVAC KIKOH Co., Ltd. was used. ⁇ Polymer solubility> When the test solvent was toluene, xylene, mesitylene, and tetralin, it was evaluated as “dissolved” when dissolved in any of these organic solvents, and “insoluble” when not dissolved in any of the solvents.
  • This insulating film was irradiated with 300 mJ / cm 2 of ultraviolet rays to photocrosslink the insulating film.
  • the thickness of this film was measured by Bruker DektakXT stylus profiler and a T 0. Then, 1 minute after immersion in a good solvent I ⁇ III of the glass plate the photocrosslinked insulating film is coated toluene, or the polymer, evaporate the toluene at room temperature was taken out, T 1 and measure the thickness It was. Using these measured film thicknesses, the remaining film ratio was calculated by the following equation.
  • Remaining film ratio T 1 / T 0 ⁇ 100 (%)
  • solvent I 1,3-bis (trifluoromethyl) benzene
  • solvent II a reagent manufactured by Tokyo Chemical Industry
  • solvent II Fluorinert (manufactured by 3M Japan)
  • solvent III CT-Solvent (trademark) -180 manufactured by Asahi Glass).
  • the contact angle was measured using a contact angle meter drop master DM300 manufactured by Kyowa Interface Science Co., Ltd.
  • the surface tension ⁇ s of the polymer was determined according to the following procedures (1) to (3).
  • (2) The dispersion term ( ⁇ S d ) and the polar term ( ⁇ S p ) of the surface tension of the polymer film were determined from the obtained contact angle ⁇ using the following formula.
  • partition forming mask obtained by patterning 10 square ⁇ 10 micron squares 10 ⁇ 10 cm in a 10 cm ⁇ 10 cm square with 10 in a row and 10 in a horizontal pattern was used.
  • a mask is placed on a polymer film having a thickness of 100 nm printed on a substrate, irradiated with 100 mJ / cm 2 of ultraviolet rays, and then uncrosslinked parts are washed and removed with a good solvent of the polymer to thereby remove 50 on the film.
  • a partition wall having a shape of 100 holes of ⁇ 50 ⁇ m 2 size was formed.
  • Example 1 Synthesis of 7-methacryloyloxy-4-oxo-benzopyran (7MOB) A stirrer was placed in a 100 mL two-necked flask equipped with a nitrogen inlet tube, 5 g of 7-hydroxy-4-oxo-benzopyran, dehydrated pyridine 4.9 g and 4-dimethylaminopyridine 0.8 g were charged. Next, 50 mL of dehydrated THF was charged and stirred at room temperature to obtain a uniform solution. After cooling the resulting solution with ice, 6.0 mL of methacryloyl chloride was slowly added using a syringe. After the addition, the reaction was allowed to proceed for 1 hour under ice cooling and 2 hours at room temperature.
  • 7MOB 7-methacryloyloxy-4-oxo-benzopyran
  • the obtained solid was recrystallized from ethanol to obtain 3.8 g of the intended 7-methacryloyloxy-4-oxo-benzopyran (7MOB).
  • the obtained 1 MO-NMR chart of 7MOB is shown in FIG. 2, and the 13 C-NMR chart is shown in FIG.
  • the reaction solution was poured into a dilute hydrochloric acid aqueous solution, and further 100 mL of chloroform was added and stirred sufficiently, and then transferred to a separatory funnel to separate the chloroform layer.
  • the remaining aqueous layer was extracted three times with chloroform, and all the chloroform solutions were combined and concentrated by an evaporator to obtain a reddish brown oil.
  • the oily product was separated by silica gel column chromatography using ethyl acetate as a mobile phase to obtain 0.06 g of 7-vinyl-4-oxo-benzopyran (7VOB) as yellow crystals.
  • FIG. 4 shows a 1 H-NMR chart of the obtained 7VOB.
  • a 2-butanol solution (5 wt%) of polymer 1 was spin-coated on the organic semiconductor layer under conditions of 500 rpm ⁇ 5 seconds and 1000 rpm ⁇ 20 seconds, and dried at 100 ° C. for 10 minutes.
  • a contact hole mask was used for this element, a UV light intensity of 4 kW / cm 2 was used, UV irradiation was performed at room temperature for 5.4 seconds, and photocrosslinking was performed at a UV irradiation amount of 300 mJ / cm 2 .
  • a gate insulating layer was formed. Further, a silver electrode having a thickness of 30 nm was vacuum deposited on the gate insulating layer using a mask. Next, this element was immersed in toluene for 1 minute to form a contact hole, and a top gate / bottom contact (TGBC) type organic transistor element was produced. Table 1 shows the evaluation results and the like of the manufactured organic transistor.
  • Polymer 1 was photocrosslinked with a low UV dose, and it was confirmed that an insulating layer having excellent solvent resistance was formed, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.
  • Example 6 0.78 g of isobutyl methacrylate, 0.23 g of 7MOB, 5.0 g of DMF, and 109 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 68 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and precipitated. The precipitate was filtered and dried under reduced pressure to obtain 0.55 g of Polymer 2. The resulting polymer 2 contained 19 mol% 7-methacryloyloxy-4-oxo-benzopyran units.
  • a top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to the polymer 2.
  • An evaluation result etc. are shown according to Table 1.
  • Polymer 2 was photocrosslinked at a low UV irradiation amount, and it was confirmed that an insulating layer having excellent solvent resistance was formed, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.
  • Example 7 0.86 g of isobutyl methacrylate, 0.15 g of 7MOB, 5.0 g of DMF, and 108 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 68 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and precipitated. The precipitate was filtered and dried under reduced pressure to obtain 0.67 g of Polymer 3. The resulting polymer 3 contained 12 mol% 7-methacryloyloxy-4-oxo-benzopyran units.
  • the polymer 3 was photocrosslinked with a low UV irradiation amount to form an insulating layer with excellent solvent resistance, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.
  • Example 8 0.86 g of isobutyl methacrylate, 0.15 g of 7MOB, 5.0 g of DMF, and 108 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 68 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and precipitated. The precipitate was filtered and dried under reduced pressure to obtain 0.68 g of Polymer 4. The resulting polymer 4 contained 16 mol% 7-methacryloyloxy-4-oxo-benzopyran units.
  • a top gate / bottom contact (TGBC) type organic transistor was fabricated in the same manner as in Example 5 except that the polymer 1 was changed to the polymer 4.
  • An evaluation result etc. are shown according to Table 1.
  • the polymer 4 was photocrosslinked with a low UV irradiation amount to form an insulating layer having excellent solvent resistance, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.
  • Example 9 0.77 g of isobutyl methacrylate, 0.23 g of 7VOB, 5 g of DMF, and 11 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 65 ° C. for 6 hours under a nitrogen seal. The obtained polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer, isolated by filtration, and then dried under reduced pressure to obtain 0.6 g of polymer 5. The resulting polymer 5 contained 26 mol% 7-vinyl-4-oxo-benzopyran units.
  • a top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to the polymer 5.
  • An evaluation result etc. are shown according to Table 1.
  • the polymer 5 was photocrosslinked at a low UV irradiation amount to form an insulating layer having excellent solvent resistance, and the formation of contact holes was easy. In addition, it was confirmed that the produced organic transistor had a small leakage current and an excellent insulating property.
  • Example 1 A top gate / bottom contact (TGBC) type organic transistor was prepared in the same manner as in Example 5 except that the polymer 1 was changed to poly (n-butyl methacrylate) (PNBMA). PNBMA was not photocrosslinked by ultraviolet rays, and it was confirmed that the flatness of the film surface was lost due to heat when vacuum-depositing the source electrode and the drain electrode. Moreover, there was no solvent resistance, and the PNBMA film was dissolved at the time of contact hole formation, so that an organic transistor element could not be produced. Table 1 shows the evaluation results.
  • PNBMA poly (n-butyl methacrylate)
  • Example 2 A top gate / bottom contact (TGBC) type organic transistor was fabricated in the same manner as in Example 5 except that the polymer 1 was changed to poly (n-octyl methacrylate) (PNOMA). It was confirmed that PNOMA was not photocrosslinked by ultraviolet rays, and the flatness of the film surface was lost due to the heat when vacuum-depositing the source electrode and the drain electrode. Further, the organic transistor element was not able to be produced because it had no solvent resistance and the PNOMA film was dissolved when the contact hole was formed. Table 1 shows the evaluation results.
  • PNOMA poly (n-octyl methacrylate)
  • Example 3 A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to polyvinyl butyral (PVB).
  • the PVB resin was not photocrosslinked by ultraviolet rays and did not exhibit solvent resistance. Further, the PVB film was not dissolved in toluene, and when butanol was used, the PVB film was dissolved and a contact hole could not be formed.
  • An evaluation result etc. are shown according to Table 1.
  • Example 4 A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to polyvinyl alcohol (PVA). PVA was not photocrosslinked by ultraviolet rays and did not exhibit solvent resistance. Further, the PVA film was not dissolved in toluene, and when butanol was used, the PVA film was dissolved and a contact hole could not be formed. An evaluation result etc. are shown according to Table 1.
  • Example 5 A top gate / bottom contact (TGBC) type organic transistor was produced in the same manner as in Example 5 except that the polymer 1 was changed to a fluorine-based cyclic ether polymer (Cytop). Cytop was not photocrosslinked by ultraviolet rays and did not exhibit solvent resistance. The Cytop film was not dissolved in toluene, and when the fluorinated solvent CYTOP CT-SOLV180 was used, the Cytop film was dissolved and a contact hole could not be formed. An evaluation result etc. are shown according to Table 1.
  • Example 6 The solubility and solvent resistance were evaluated in the same manner as in Example 5 except that the polymer 1 was used and ultraviolet rays were not irradiated. Polymer 1 was dissolved in n-butanol, and the residual film ratio was 0. ⁇ Production and evaluation of organic transistor element> A top gate / bottom contact (TGBC) type organic transistor was fabricated in the same manner as in Example 5. The polymer 1 did not have solvent resistance, the entire film was dissolved, and a contact hole could not be formed. An evaluation result etc. are shown according to Table 1.
  • Example 10 2 g of styrene, 0.78 g of 7MOB, 14 g of DMF, and 39 mg of AIBN were charged into a 20 ML Schlenk tube, sufficiently deaerated, and then polymerized at 65 ° C. for 6 hours under a nitrogen seal.
  • the obtained polymer solution was poured into 300 mL of methanol under stirring to precipitate the polymer, isolated by filtration, and then dried under reduced pressure to obtain 0.4 g of polymer 6.
  • the resulting polymer 6 contained 28 mol% 4-oxo-benzopyran units (formula (4)) and 72 mol% styrene monomer units (formula (7)).
  • a 1 H-NMR chart of the obtained polymer 6 is shown in FIG.
  • UV irradiation is performed at room temperature for 5.4 seconds, and crosslinking is performed under the condition of an ultraviolet irradiation amount of 300 mJ / cm 2.
  • Gold was vacuum-deposited on the substrate on which the gate electrode and the polymer dielectric layer were formed to form a source electrode and a drain electrode having a thickness of 50 nm, a channel length of 100 ⁇ m, and an electrode width of 500 ⁇ m.
  • Example 11 A 25 mL Schlenk tube was charged with 0.3 g of BOBF obtained in Example 3, 0.012 g of azoisobutyronitrile (AIBN), 0.7 g of styrene, and 7.5 g of N-methylpyrrolidone, and freeze degassing with liquid nitrogen. And dissolution was repeated 4 times, followed by polymerization at 73 ° C. for 6 hours under nitrogen pressure. After completion of the polymerization, the reaction solution was poured into 100 mL of methanol to precipitate a polymer, filtered and washed with methanol, and then dried at 50 ° C. to obtain 0.5 g of light brown polymer 7.
  • AIBN azoisobutyronitrile
  • the resulting polymer 7 had 4 mol% of BOBF-derived repeating units (formula (5)) and 96 mol% of styrene units (formula (7)).
  • a 1 H-NMR chart of the obtained polymer 7 is shown in FIG.
  • Table 2 shows the results and the like of an organic transistor element prepared and evaluated in the same manner as in Example 10 except that the polymer 6 was changed to the polymer 7.
  • Example 12 7MOB 0.35g, THF 14g, and AIBN 17.5mg were charged into a 20ML Schlenk tube and sufficiently deaerated, and then PFS 1.65g was charged in a nitrogen box. After sufficiently performing nitrogen substitution again, polymerization was performed at 60 ° C. for 6 hours under a nitrogen seal. The obtained polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer, isolated by filtration, and then dried under reduced pressure to obtain 0.4 g of polymer 8.
  • the resulting polymer 8 comprises 16 mol% 4-oxo-benzopyran units (formula (4)) and 84 mol% 2,3,4,5,6-pentafluorostyrene styrene (PFS) monomer units ( (7)).
  • a 1 H-NMR chart of the obtained polymer 8 is shown in FIG.
  • Table 2 shows the results obtained by producing an organic transistor element in the same manner as in Example 10 except that the polymer 6 is changed to the polymer 8.
  • Example 13 1.0 g of styrene, 0.78 g of 7MOB, 18 g of THF, and 39 mg of AIBN were charged into a 20 ML Schlenk tube and sufficiently deaerated, and then 1.86 g of PFS was charged in a nitrogen box. After sufficiently performing nitrogen substitution again, polymerization was performed at 60 ° C. for 6 hours under a nitrogen seal. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration.
  • the filtered polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring and precipitated, and the precipitate was filtered and dried under reduced pressure to obtain 0.5 g of polymer 9.
  • the obtained polymer 9 was composed of 21 mol% of 4-oxo-benzopyran unit (formula (4)), 42 mol% of 2,3,4,5,6-pentafluorostyrene monomer unit (formula (7) ) And 37 mol% of styrene monomer units (formula (7)) (formula (7) is mol% in total).
  • Table 2 shows the results obtained by producing and evaluating an organic transistor element in the same manner as in Example 10 except that the polymer 6 is changed to the polymer 9.
  • Example 14 A 20-ML Schlenk tube was charged with 0.232 g of 7VOB, 0.708 g of styrene, 14 mg of AIBN, and 5 g of dimethylformamide. After nitrogen substitution, polymerization was performed at 60 ° C. for 6 hours under nitrogen pressure. The resulting polymer solution was poured into 300 mL of methanol with stirring to precipitate the polymer and isolated by filtration. The obtained polymer was dissolved in 10 mL of methylene chloride, poured into 300 mL of methanol with stirring, and reprecipitated. Then, the precipitate was filtered and dried under reduced pressure to obtain 0.6 g of the polymer 10. The resulting polymer 10 contained 35 mol% 4-oxo-benzopyran units (formula (43)) and 37 mol% styrene monomer units (formula (7)).
  • Table 2 shows the results of producing and evaluating an organic transistor element in the same manner as in Example 10 except that the polymer 6 was changed to the polymer 10.
  • Example 7 Solubility, UV crosslinkability, and solvent resistance were evaluated in the same manner as in Example 10 except that the polymer 6 was changed to an FCE polymer (Cytop, manufactured by AGC Asahi Glass Co., Ltd.).
  • the FCE polymer did not dissolve in any of the test solvents and could not be formed using a general-purpose solvent. Moreover, it was dissolved in the fluorine-based solvent PFTBA and irradiated with UV, but it was not crosslinked, and the remaining film ratio with respect to this solvent was 0. Accordingly, UV irradiation to the FCE polymer layer was omitted, and an organic transistor device was produced in the same manner as in Example 10.
  • the nitrogen flow to the Schlenk tube was stopped, the three-way cock at the top of the dropping funnel was connected to the calcium chloride tube, and then the nitrogen flow was stopped.
  • the Schlenk tube was cooled with ice water, and cinnamic acid chloride was dropped from the dropping funnel over 10 minutes. The color of the polymer solution colored reddish purple as it was dropped.
  • the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 28 hours.
  • the reaction solution was cooled again with ice water, and 20 ml of 35% aqueous hydrochloric acid was added dropwise. After stirring in this state for 5 hours, the reaction solution was transferred to a separatory funnel, and the methylene chloride layer was separated.
  • Example 11 The polymer 6 obtained in Example 10 was used, and the solubility and solvent resistance were evaluated by the same method as in Example 10 except that ultraviolet rays were not irradiated. The polymer 6 was dissolved in the test solvent and the remaining film rate was 0.
  • Example 15 In a nitrogen box, put a magnetic stir bar in a 20 ML Schlenk tube, 7.1 mg of azobisisobutyronitrile (AIBN), monomer with inhibitor removed (0.27 g of 6CHMA, and 1H, 1H, 2H, 2H -Heptadecafluorodecyl methacrylate (HFDMA) (1.73 g), toluene (4.3 g), ⁇ , ⁇ , ⁇ , ⁇ ', ⁇ ', ⁇ '-hexafluoro-m-xylene (HFMX) (7 g), Gas (freezing with liquid nitrogen, degassing, thawing by heating) was performed 4 times.
  • AIBN azobisisobutyronitrile
  • FIG. 11 shows a 1 H-NMR chart of the polymer 12 measured by dissolving it in a mixed solvent of deuterated chloroform and HFMX.
  • the polymer 12 was dissolved in the solvent I, spin-coated on a glass plate, and the solvent resistance, contact angle, and surface tension of the UV-crosslinked polymer film were measured.
  • the polymer 12 was dissolved in the solvent I to form a polymer film having excellent solvent resistance at room temperature and a UV irradiation amount of 100 mJ / cm 2 .
  • the outstanding liquid repellency with respect to water and tetralin was shown.
  • the solvent I to III had a small contact angle and excellent wettability, but did not dissolve and had excellent solvent resistance.
  • Parylene-C manufactured by Japan Parylene Godo Kaisha
  • SCS Lab Coater 2 manufactured by Japan Parylene Godo Kaisha (model PDS2010)
  • base material base material
  • a film was formed by a vacuum evaporation method to form an insulating layer 1 having a thickness of 300 nm (substrate 1).
  • Gold was vacuum-deposited on this substrate (1) to form a source electrode and a drain electrode having a thickness of 50 nm, a channel length of 50 ⁇ m, and an electrode width of 50 ⁇ m.
  • a HFMX solution (2 wt%) of the polymer 12 was spin-coated on the substrate 2 under conditions of 500 rpm ⁇ 5 seconds and 1000 rpm ⁇ 20 seconds to form a polymer film having a thickness of 100 nm.
  • the polymer film was crosslinked by irradiating with 100 mJ / cm 2 ultraviolet rays through a partition wall forming mask, and washed with HFMX to remove uncrosslinked portions (substrate 3).
  • Example 16 In a nitrogen box, a magnetic stirrer was placed in a 20-ML Schlenk tube, 6.6 mg of AIBN, and the monomer from which the inhibitor was removed (6CHMA 0.24 g, and 1H, 1H, 2H, 2H-heptadecafluoro Decyl methacrylate (HFDMA) 1.76 g), toluene 3.0 g, ⁇ , ⁇ , ⁇ , ⁇ ′, ⁇ ′, ⁇ ′-hexafluoro-m-xylene (HFMX) 4.9 g, and then deaerated ( Freezing with liquid nitrogen, deaeration, and thawing by heating) were performed 4 times.
  • HFDMA 1H, 1H, 2H, 2H-heptadecafluoro Decyl methacrylate
  • HMFX ⁇ ′-hexafluoro-m-xylene
  • Example 17 In a nitrogen box, put a magnetic stir bar in a 20 ML Schlenk tube, AIBN 6.8 mg, monomer with inhibitor removed (6CHMA 0.34 g, and 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (HFDMA) 1.66 g), 3.0 g of toluene, 4.9 g of ⁇ , ⁇ , ⁇ , ⁇ ′, ⁇ ′, ⁇ ′-hexafluoro-m-xylene (HFMX), and then degassed (freeze with liquid nitrogen, Degassing and melting by heating) were performed 4 times. Under stirring, the mixture was heated under nitrogen pressure and polymerized at 60 ° C. for 6 hours.
  • HFDMA monomer with inhibitor removed
  • a polymerization inhibitor (BHT) solution was added to the Schlenk tube and stirred for 1 minute, and then cooled to room temperature.
  • the obtained reaction solution was poured into a 500 mL methanol solution to precipitate a polymer, and vacuum dried at 50 ° C. to obtain 0.9 g of the polymer 14.
  • the resulting polymer 14 contained 75 mol% HFDMA units and 25 mol% 6CHMA units.
  • Resins suitable for forming insulating layers for high-quality organic transistor devices that can be manufactured by printed electronics technology can be provided.
  • A Bottom gate-top contact type organic transistor
  • B Bottom gate-bottom contact type organic transistor
  • C Top gate-top contact type organic transistor
  • D Top gate-bottom contact type organic transistor 1: Organic semiconductor layer 2: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Thin Film Transistor (AREA)

Abstract

L'invention concerne : un polymère pour former une couche isolante dans laquelle des trous de contact peuvent être formés, où le polymère se dissout dans un alcool aliphatique inférieur et réticule en un court laps temps sous l'action de rayons ultraviolets ; un polymère qui peut être utilisé comme couche isolante dans un dispositif à transistor organique, se dissout dans des solvants à usage général, réticule à température normale et en court laps de temps, et présente d'excellentes propriétés isolantes ; et un polymère qui est soluble dans un solvant, peut devenir insoluble dans un solvant par photoréticulation à température normale en un court de laps de temps, et est hydrofuge. L'invention concerne également un composé polymérisable représenté par la formule (1) et la formule (2). (Dans la formule (1) : R1 est un atome d'hydrogène ou un groupe alkyle en C1-C6 ; L est un groupe de liaison divalent en C1-C14 ; n est 0 ou 1 ; A, R2 et R3 sont chacun indépendamment choisis dans le groupe constitué par un atome d'hydrogène, les halogènes, les groupes cyano, les groupes nitro, les groupes alkyle en C1-C18, les groupes alcoxy, les groupes alkylthio, les groupes alkylamino, les groupes alkylcétone, les groupes alkylester, les groupes alkylamido, les groupes aryle, les groupes aryléther, les groupes arylthio, les groupes carboxyalkyle, les groupes fluoroalkyle, les groupes fluoroalcoxy, les groupes fluoroalkylcarbonyle, les groupes fluoroalkylester, les groupes fluoroaryle, les groupes fluorothio, les groupes cycloalkyle, et les groupes cyclohétéroalkyle ; X est O ou S ; et m est un nombre entier de 0 à 3). (Dans la formule (2) :Q1 et Q2 sont chacun indépendamment un groupe de liaison divalent en C1-C14 ; p et q sont chacun indépendamment 0 ou 1 ; G1, G2, et R4-R7 représentent chacun indépendamment un atome d'hydrogène, un halogène, un groupe cyano, un groupe nitro, un groupe alkyle en C1-C18, un groupe alcoxy, un groupe alkylthio, un groupe alkylamino, un groupe alkylcétone, un groupe alkylester, un groupe alkylamido, un groupe aryle, un groupe aryléther, un groupe arylthio, un groupe carboxyalkyle, un groupe fluoroalkyle, un groupe fluoroalkyléther, un groupe fluoroalkylcarbonyle, un groupe fluoroalkylester, un groupe fluoroaryle, un groupe fluorothio, un groupe cycloalkyle ou un groupe cyclohétéroalkyle ; X1-X4 représentent chacun indépendamment O ou S ; et r et s sont chacun indépendamment un nombre entier de 0 à 3).
PCT/JP2019/011494 2018-03-23 2019-03-19 Composé polymérisable, polymère photodurcissable, film isolant, film de protection et dispositif à transistor organique Ceased WO2019181954A1 (fr)

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JP2018-057039 2018-03-23
JP2018057039 2018-03-23
JP2018-092191 2018-05-11
JP2018092191 2018-05-11
JP2018128598A JP7283035B2 (ja) 2018-07-05 2018-07-05 重合体、絶縁膜、撥液膜、及び電子デバイス
JP2018-128598 2018-07-05
JP2019044889A JP7371334B2 (ja) 2018-05-11 2019-03-12 重合性化合物、光架橋性重合体、絶縁膜、及び有機トランジスタデバイス
JP2019-044889 2019-03-12
JP2019-044884 2019-03-12
JP2019044884A JP7363060B2 (ja) 2018-03-23 2019-03-12 重合性化合物、光硬化型重合体、絶縁膜、保護膜、及び有機トランジスタデバイス

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426750A (zh) * 2020-10-29 2022-05-03 秀昌有限公司 液晶高分子组成物及绝缘膜

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4817273B1 (fr) * 1966-09-19 1973-05-28
US20030073028A1 (en) * 2001-08-30 2003-04-17 Clean Creative Co. Ltd. Organic polymers for bottom antireflective coating, process for preparing the same, and compositions containing the same
JP2018018928A (ja) * 2016-07-27 2018-02-01 東ソー株式会社 絶縁膜及びこれを含む有機電界効果トランジスタデバイス
JP2018154814A (ja) * 2017-03-16 2018-10-04 東ソー株式会社 光架橋性重合体、絶縁膜、平坦化膜、親撥パターニング膜及びこれを含む有機電界効果トランジスタデバイス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4817273B1 (fr) * 1966-09-19 1973-05-28
US20030073028A1 (en) * 2001-08-30 2003-04-17 Clean Creative Co. Ltd. Organic polymers for bottom antireflective coating, process for preparing the same, and compositions containing the same
JP2018018928A (ja) * 2016-07-27 2018-02-01 東ソー株式会社 絶縁膜及びこれを含む有機電界効果トランジスタデバイス
JP2018154814A (ja) * 2017-03-16 2018-10-04 東ソー株式会社 光架橋性重合体、絶縁膜、平坦化膜、親撥パターニング膜及びこれを含む有機電界効果トランジスタデバイス

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ATTILA VASAS ET AL.: "The Heck Reaction of Protected Hydroxychromones on route to Natural Products", AUSTRALIAN JOURNAL OF CHEMISTRY, vol. 64, no. 5, 2011, pages 647 - 657, XP055638200 *
BO - LIANG DENG ET AL.: "Synthesis of 7 - Vinylflavone and 7 - Aminoflavone by Palladium - Catalyzed Coupling Reactions", EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, vol. 1999, no. 10, October 1999 (1999-10-01), pages 2683 - 2688, XP055638202 *
KWANG-DUK AHN ET AL.: "New Antireflective Coating Materials Containing a Novel Chromophore for KrF Laser Lithography", JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY, vol. 14, no. 3, 2001, pages 475 - 480, XP008050242 *
ROBERTO ARTALI ET AL.: "Synthesis, X-ray crystal structure and biological properties of acetylenic flavone derivatives, II Farmaco", INTERNATIONAL JOURNAL OF MEDICINAL CHEMISTRY AND PHARMACEUTICAL CHEMISTRY, vol. 58, no. 9, 2003, pages 875 - 881, XP055638201 *
THIRUPATHI GOGULA ET AL.: "Synthesis of Diverse Oxa - Carbocycle - Annulated Flavones Using the Combined Claisen Rearrangement and Ring - Closing Metathesis", HELVETICA CHIMICA ACTA, vol. 99, no. 7, 2016, pages 547 - 557, XP055638203 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426750A (zh) * 2020-10-29 2022-05-03 秀昌有限公司 液晶高分子组成物及绝缘膜

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