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WO2018168676A1 - Polymère photoréticulable, film isolant, film aplati, et film à motif d'attraction/répulsion ainsi que dispositif de transistor organique à effet de champ contenant celui-ci - Google Patents

Polymère photoréticulable, film isolant, film aplati, et film à motif d'attraction/répulsion ainsi que dispositif de transistor organique à effet de champ contenant celui-ci Download PDF

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Publication number
WO2018168676A1
WO2018168676A1 PCT/JP2018/009167 JP2018009167W WO2018168676A1 WO 2018168676 A1 WO2018168676 A1 WO 2018168676A1 JP 2018009167 W JP2018009167 W JP 2018009167W WO 2018168676 A1 WO2018168676 A1 WO 2018168676A1
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WIPO (PCT)
Prior art keywords
group
formula
resin
film
effect transistor
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PCT/JP2018/009167
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English (en)
Japanese (ja)
Inventor
山川浩
奥慎也
弓野翔平
李廷輝
片桐史章
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Tosoh Corp
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Tosoh Corp
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Publication date
Priority claimed from JP2017199489A external-priority patent/JP6953986B2/ja
Priority claimed from JP2018011579A external-priority patent/JP6992545B2/ja
Priority claimed from JP2018011580A external-priority patent/JP6992546B2/ja
Application filed by Tosoh Corp filed Critical Tosoh Corp
Priority to US16/494,107 priority Critical patent/US12291587B2/en
Priority to EP18767508.7A priority patent/EP3597673B1/fr
Priority to CN201880017891.8A priority patent/CN110418808B/zh
Publication of WO2018168676A1 publication Critical patent/WO2018168676A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/10—Acylation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • 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 forms a film having excellent flatness by coating in a solution state, easily crosslinks by light irradiation for a short time, and has solvent resistance (crack resistance) but also wettability to solvent (
  • the present invention relates to a resin having excellent overcoat property and high dielectric breakdown strength.
  • Dielectric breakdown strength refers to the maximum electric field value that can be applied without destroying the dielectric layer that constitutes the device. The higher the dielectric breakdown strength, the higher the stability of the device.
  • the leakage current is an index indicating the magnitude of a current other than the original conductive path, for example, a current flowing from the gate electrode through the insulating dielectric layer to the source electrode.
  • the leakage current is obtained by preparing a MIM capacitor having a three-layer structure of metal / dielectric / metal and measuring the value of current flowing in the dielectric layer.
  • a polymer dielectric layer is an overlay layer such as an organic semiconductor layer. Laminated. Therefore, when an overlay layer is formed on a polymer dielectric layer by a printing method using a solvent, the polymer dielectric must not be dissolved in this solvent (a solvent used in the printing method). . Therefore, the polymer dielectric layer (insulating film layer) must be dissolved in a general-purpose organic solvent when forming the layer, and insoluble in the organic solvent after forming the layer. Conflicting performance is required.
  • a technique for crosslinking a polymer dielectric layer formed by solution film formation is known.
  • benzocyclobutene resin and polyvinyl phenol resin are known.
  • a benzocyclobutene resin has a high crosslinking temperature of 250 ° C. and a plastic is used as a base material, the base material is thermally deformed. It was difficult and the curing time was long and the economy was poor. Furthermore, it is extremely difficult to apply to the roll-to-roll process, and the flatness of the film that affects the device performance is not sufficient.
  • Polyvinylphenol uses a melamine resin or the like as a cross-linking agent and requires a long curing reaction at a temperature of about 150 ° C., and is extremely difficult to apply to a roll-to-roll process.
  • the hydroxyl groups of the polyvinylphenol resin do not disappear completely, and there is a problem of high leakage current estimated to be caused by hydrophilicity due to the remaining hydroxyl groups.
  • the flatness of the film was not sufficient.
  • fluorine-based cyclic ether resin polyparaxylylene resin, or the like as a type of resin that does not require crosslinking used for the polymer dielectric layer (insulating film layer)
  • the fluorine-based cyclic ether resin does not dissolve in a general-purpose organic solvent after film formation, it has an advantage that it is insoluble in a general-purpose solvent even if it is not crosslinked, but is inferior in economic efficiency.
  • this material has a low surface tension, the wettability with respect to the base material is poor, and the base material that can be coated or printed has a great restriction.
  • Polyparaxylylene resin has the advantage that it is not dissolved in a general-purpose solvent because it is deposited on a substrate by vapor deposition and polymerized on the substrate by vacuum deposition. It has a fatal defect that it cannot respond.
  • Photocrosslinking technology is known as a means that can be crosslinked at a low temperature and shortens the crosslinking time.
  • it has photocrosslinkability such as cinnamoyl group for polymers having hydroxyl groups in the side chain such as poly (hydroxyethyl methacrylate), vinylphenol-methyl methacrylate copolymer, polyacetoxyethyl methacrylate, polyhydroxyethyl methacrylate, etc.
  • a technique of using a photocrosslinkable polymer obtained by reacting a compound having a polymer dielectric as a polymer dielectric is disclosed (for example, see Patent Document 1).
  • Patent Document 1 also discloses a technique for reducing the amount of residual hydroxyl groups by reacting unreacted hydroxyl groups with trifluoroacetic anhydride for esterification.
  • it is extremely difficult to completely eliminate the hydroxyl group, and there is a problem that the wettability with respect to the organic solvent is lowered by the introduction of the fluorine compound.
  • Non-Patent Document 1 a technique using poly (vinyl cinnamate) as a polymer dielectric layer of an organic field effect transistor device has been proposed (see, for example, Non-Patent Document 1 and Non-Patent Document 2), but the solution was applied.
  • the flatness of the polymer dielectric layer (insulating film layer) is about 0.7 nm, and further flattening has been demanded.
  • a compound having a photoreactive group is introduced into an aromatic vinyl polymer such as polystyrene or poly- ⁇ -methylstyrene by Friedel-Crafts acylation reaction.
  • a technique related to the photosensitive resin is disclosed in the 1950s. However, this technique has a problem that the resin gels during the manufacturing process if a large number of photoreactive groups are introduced to shorten the exposure time. Therefore, the introduction amount of the photoreactive group needs to be less than 17 mol% with respect to the total number of moles of monomers constituting the polymer (for example, see Patent Document 3 and Patent Document 4).
  • the concentration of the photoreactive group is small, and thus the crosslink density of the photocrosslinked film is low.
  • the crosslinked film absorbs the solvent and swells.
  • the present invention has been made in view of the above problems, and its purpose is solubility in general-purpose solvents, crosslinking temperature, time required for crosslinking, solvent resistance (crack resistance), wettability to solvents, leakage current,
  • An object of the present invention is to provide a resin capable of producing a polymer dielectric layer (insulating film layer) having excellent performance in terms of dielectric breakdown strength.
  • the present inventors have found that a specific resin is soluble in a general-purpose solvent required for an insulating film, a crosslinking temperature, a time required for crosslinking, and solvent resistance (crack resistance).
  • the present invention has been completed by finding that it has excellent wettability to solvent, leakage current, and dielectric breakdown strength.
  • R 1 represents hydrogen or a C1-C6 alkyl group
  • S 1 represents —O— or —C (O) —
  • p represents 0 or 1
  • a 1 represents a C6-C19 aryl.
  • Y represents a halogen, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group
  • k represents 0 to (s-1 Where s represents the number of carbon atoms constituting A 1.
  • R 2 represents hydrogen or a C1-C6 alkyl group
  • S 2 represents —O— or —C (O) —
  • q represents 0 or 1
  • a 2 represents C6 to C19.
  • Y represents an aryl group
  • Y represents a substituent defined in formula (1)
  • j represents an integer of 0 to (r-2)
  • m represents an integer of 1 to (rj-1), where r Represents the number of carbon atoms constituting A 2.
  • Z represents at least one organic group selected from formulas (A) to (D).
  • R 3 and R 4 each independently represent hydrogen, a C1-C6 alkyl group, an aryl group, or a carboxyalkyl group
  • R 5 to R 29 each independently represent Represents hydrogen, halogen, cyano group, carboxyalkyl group, alkyl ether group, aryl ether group, C1-C18 alkyl group, fluoroalkyl group, or cycloalkyl group
  • An insulating film comprising the cross-linked product of the resin according to [1].
  • the gate insulating layer is described in [2] above.
  • An organic field effect transistor device characterized by being an insulating film.
  • a planarization film comprising the resin according to [1] and / or the crosslinked product of the resin according to [1].
  • a hydrophilic / repellent patterning film comprising the resin according to [1] and / or a crosslinked product of the resin according to [1].
  • the resin of the present invention contains repeating units of the above formula (1) and the above formula (2).
  • R 1 represents hydrogen or a C1-C6 alkyl group.
  • 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.
  • S 1 represents —O— or —C (O) —.
  • p 0 or 1.
  • a 1 represents a C6 to C19 aryl group.
  • the C6 to C19 aryl group in A 1 in the formula (1) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • Y represents a halogen, a cyano group, a carboxyalkyl group, an alkyl ether group, an aryl ether group, a C1-C18 alkyl group, a fluoroalkyl group, or a cycloalkyl group.
  • halogen in Y in Formula (1) For example, chlorine, a fluorine, etc. are mentioned.
  • the alkyl ether group for Y in the formula (1) is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group.
  • the aryl ether group in Y in the formula (1) is not particularly limited, and examples thereof include a phenoxy group, 4-methylphenoxy group, 4-tert-butylphenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like. .
  • the C1-C18 alkyl group for Y 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.
  • the fluoroalkyl group for Y in formula (1) is not particularly limited, and examples thereof include 1,1,1-trifluoroethyl group, 1,1,1,2,2-pentafluoropropyl group, 1,1,1, Examples include 1,2,2,3,3-heptafluorobutyl group.
  • the cycloalkyl group for Y in the formula (1) is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.
  • k is an integer of 0 to (s-1). To express.
  • s represents the number of carbon atoms constituting the A 1.
  • R 2 represents hydrogen or a C1-C6 alkyl group.
  • the C1-C6 alkyl group in R 2 in the formula (2) 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.
  • S 2 represents —O— or —C (O) —.
  • q 0 or 1.
  • a 2 represents a C6 to C19 aryl group.
  • the C6 to C19 aryl group in A 2 in Formula (2) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • Y represents a substituent similar to the substituent defined in formula (1).
  • m represents an integer of 1 to (r ⁇ j ⁇ 1).
  • r represents the number of carbon atoms constituting A 2
  • j represents an integer of 0 to (r ⁇ 2).
  • Z represents at least one organic group selected from formulas (A) to (D).
  • R 3 and R 4 each independently represent hydrogen, a C1-C6 alkyl group, an aryl group, or a carboxyalkyl group
  • R 5 to R 29 each independently It represents hydrogen, halogen, cyano group, carboxyalkyl group, alkyl ether group, aryl ether group, C1-C18 alkyl group, fluoroalkyl group, or cycloalkyl group.
  • the C1-C6 alkyl group in R 3 and R 4 in the formulas (A) to (D) 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. Etc.
  • the aryl group in R 3 and R 4 in the formulas (A) to (D) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • the carboxyalkyl group for R 3 and R 4 in formulas (A) to (D) is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, and a carboxypropyl group.
  • the halogen in R 5 to R 29 in the formulas (A) to (D) is not particularly limited, and examples thereof include chlorine and fluorine.
  • the carboxyalkyl group in R 5 to R 29 in the formulas (A) to (D) is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, and a carboxypropyl group.
  • the alkyl ether group in R 5 to R 29 in the formulas (A) to (D) is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group. .
  • the aryl ether group in R 5 to R 29 in the formulas (A) to (D) is not particularly limited, and examples thereof include a phenoxy group, a p-methylphenoxy group, a p-ethylphenoxy group, and a p-methoxyphenoxy group. Is mentioned.
  • the alkyl group of C1 to C18 in R 5 to R 29 in the formulas (A) to (D) 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. N-hexyl group, n-decyl group, n-octadecyl group and the like.
  • the fluoroalkyl group for R 5 to R 29 in the formulas (A) to (D) is not particularly limited, and examples thereof include 1,1,1-trifluoroethyl group, 1,1,1,2,2- Examples thereof include a pentafluoropropyl group and a 1,1,1,2,2,3,3-heptafluorobutyl group.
  • the cycloalkyl group in R 5 to R 29 in the formulas (A) to (D) is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • organic group represented by the formula (A) include the following.
  • organic group represented by the formula (B) include the following.
  • organic group represented by the formula (C) include the following.
  • organic group represented by the formula (D) include the following.
  • the polymer containing the repeating unit of the specific formula (1) and formula (2) used in the present invention contains an aromatic group and contains a hydroxyl group, an amino group, a thiol group and the like that react with an acid chloride. If not, it can be used without any restrictions.
  • the molecular weight of the resin having the repeating unit of the above formula (1) and the above formula (2) for example, those having 200 to 10,000,000 (g / mol).
  • it is preferably 10,000 to 1,000,000 (g / mol).
  • the resin having repeating units of the above formulas (1) and (2) used in the present invention can be obtained by introducing a photocyclizable compound into an aromatic group-containing polymer by Friedel-Crafts acylation reaction.
  • the photocyclization compound is introduced into a film in a certain amount or more, so that the film has excellent flatness and can be photocrosslinked in a short time. It is inferior in flatness only and cannot be photocrosslinked.
  • the photocyclizable compound is represented by the cinnamic acid chloride compound represented by the following formula (3), the phenylethenylbenzoic acid chloride compound represented by the following formula (4), and the following formula (5).
  • Pyridinylethenylbenzoic acid chloride and coumarin-6-carboxylic acid chloride represented by the following formula (6) are shown.
  • cinnamic acid chloride which is easy to produce, is preferably used.
  • these compounds can also use 2 or more types together as needed.
  • the amount of the above-mentioned acid chloride charged in the resin having the repeating unit of the formula (1) and the formula (2) is the aromatic contained in the resin in order to improve the solubility of the resulting resin in the organic solvent and the storage stability.
  • the amount is preferably 0.2 to 2.0 mol, more preferably 0.2 to 1.5 mol, per 1 mol of the group.
  • the amount of photoreactive groups introduced into the aromatic group in the reaction is the solubility in organic solvents, storage stability, ease of photocrosslinking, and solvent resistance (crack resistance) of the resin layer after photocrosslinking. From this point of view, the amount is preferably 0.2 to 1.0 mol, more preferably 0.2 to 0.7 mol with respect to 1 mol of the aromatic group contained in the resin.
  • the aromatic group-containing polymer into which the photoreactive group is introduced by Friedel-Crafts acylation reaction is not limited as long as it is inactive with respect to the reaction catalyst described later.
  • poly- ⁇ -methylstyrene Polystyrene, such as poly-p-methoxystyrene and syndiopolystyrene; polyvinyl naphthalene; polyvinyl biphenyl; polyvinyl anthracene; polyvinyl carbazole; polyvinyl aryl ketone such as polyvinyl phenyl ketone; styrene butadiene copolymer; ethylene / styrene copolymer; ⁇ Acrylonitrile copolymer; Styrene / alkyl acrylate copolymer; Styrene / alkyl methacrylate copolymer; Styrene / ⁇ -phenylalkyl acrylate copolymer;
  • a polymer composed only of an aromatic hydrocarbon and an aliphatic hydrocarbon is used. Is preferred. Moreover, these copolymers can also be used in combination of 2 or more types.
  • the Friedel-Crafts acylation reaction can be carried out using a reaction catalyst.
  • a known super strong acid can be used as a reaction catalyst, and there is no limitation as long as it is a super strong acid, and examples thereof include trifluoromethane sulfonic acid, fluorosulfonic acid, fluoroantimonic acid, and carborane acid.
  • the addition amount of the catalyst is 0.1 to 1.5 times mol of the above acid chloride in order to avoid complicated neutralization after the reaction and to prevent the reaction rate from decreasing. Is preferred.
  • the Friedel-Crafts acylation reaction is an exothermic reaction and may cause a side reaction in which the photoreactive group is crosslinked by heating in this reaction system. Therefore, in the present invention, in order to suppress the side reaction, it is preferable to carry out by a solution reaction in which the reaction temperature can be easily controlled.
  • the reaction solvent used in the solution reaction in the present invention can be used without any limitation as long as it is stable against the Friedel-Crafts reaction, and is sufficiently dehydrated chlorine-based hydrocarbon solvent, aliphatic carbonization which is inert to the reaction.
  • a hydrogen solvent, a sulfur-containing solvent, a nitrile solvent or the like is preferably used.
  • chlorinated hydrocarbon solvents examples include methylene chloride, carbon tetrachloride, 1,1,2-trichloroethane, chloroform, etc., aliphatic hydrocarbon solvents such as cyclohexane, and sulfur-containing solvents such as carbon disulfide and sulfonedimethyl. Examples thereof include sulfoxide, dimethyl sulfate and dimethyl sulfone, and examples of the nitrile solvent include acetonitrile.
  • the reaction temperature is not particularly limited, but it is preferably 0 to 40 ° C. from the viewpoint of economy related to cooling and heating, and 0 to 15 ° C. from the viewpoint of suppressing the formation of microgel. Further preferred. Moreover, although it is possible to carry out at the reflux temperature of the solvent used as necessary, a temperature of less than 200 ° C. is preferred.
  • the reaction time is not particularly limited, and examples thereof include 5 to 100 hours. From the viewpoint of reaction rate and economy, it is preferably 10 hours to 50 hours.
  • the resin having the repeating unit of formula (1) and formula (2) may contain a structure based on the cyclization of the photoreactive group in the polymer molecule as long as the solubility is not impaired.
  • Examples of the structure based on cyclization of the photoreactive group include structures represented by the following formulas (7) to (10).
  • R 3 , R 4 and R 10 to R 18 are the same as in Formula (4)).
  • R 3 , R 4 , R 27 to R 29 are the same as in Formula (6)
  • the resin having the repeating units of the formulas (1) and (2) may contain, for example, a dimerized photoreactive group as shown below.
  • R 3 and R 4 to R 26 are the same as those defined in Formulas (A) to (C).
  • A, b, and c) Represents an integer of 0 to 4, R A is a substituents selected from R 5 to R 9 defined in Formula (A), and R B is selected from R 14 to R 18 defined in Formula (B) B substituents, R C represents c substituents selected from R 23 to R 26 defined in formula (C).
  • Z in the formula (2) is an organic group represented by the formula (A)
  • the resins having repeating units of the formula (1) and the formula (2) are represented by the formulas (1) and (1).
  • the resin may have a repeating unit (2) and further have a repeating unit represented by the formula (18). At this time, since a part of the repeating unit of the formula (2) becomes the repeating unit of the formula (18), generation of microgel can be suppressed, and the resin is more excellent in productivity.
  • R 2 , S 2 , A 2 and Y are the substituents defined in the formula (2), q is an integer defined in the formula (2), and n is 0 to (t-4)
  • t represents the total number of carbon atoms constituting A 2.
  • d and e are located at positions ortho to each other on the aromatic group A 2 (bonded to adjacent carbon atoms).
  • R 3 to R 9 are the same as defined in formula (A).
  • n represents an integer of 0 to (t-4).
  • t represents the total number of carbon atoms constituting the A 2.
  • D and e each represent a single bond located at the position of the ortho position on the aromatic group A 2 (bonded to adjacent carbon).
  • the resin having the repeating unit of the formula (1) and the formula (2) has the repeating unit of the above formula (1) and the above formula (2), and further has the repeating unit represented by the formula (19). Resin may be used. At this time, the liquid repellency in the case of the hydrophilic / repellent patterning film is improved, and the resin becomes more excellent in resolution when the fine electrode is formed.
  • a 3 is a C6-C19 aryl group
  • Y is a substituent defined in the formula (1)
  • R 30 is hydrogen or a C1-C6 alkyl group
  • R f is a C1-C18 the fluoroalkyl group
  • v is an integer of 0 ⁇ (u-2)
  • w represents an integer of 1 ⁇ (u-v-1 ).
  • u represents the number of carbon atoms constituting the a 3.
  • a 3 represents a C6 to C19 aryl group.
  • the C6 to C19 aryl group in A 3 in Formula (19) is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group.
  • Y represents an organic group similar to the organic group defined in formula (1).
  • R 30 represents hydrogen or a C1-C6 alkyl group.
  • the C1-C6 alkyl group for R 30 in formula (19) 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.
  • R f represents a C1-C18 fluoroalkyl group.
  • the C1-C18 fluoroalkyl group in R f in the formula (19) is not particularly limited, and examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, Perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluorododecyl group, perfluorooctadecyl group and other linear perfluoroalkyl groups; perfluoroisopropyl group, perfluoro Branched perfluoroalkyl groups such as fluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, perfluoroneopentyl group; perfluorocyclopropyl group, per
  • v represents an integer of 0 to (u-2), and m represents an integer of 1 to (uv-1).
  • u represents the number of carbon atoms constituting the A 3.
  • any solvent that dissolves the resin can be used without any limitation.
  • Aromatic hydrocarbons such as: Chlorinated aliphatic hydrocarbon compounds such as methylene chloride and 1,1,2-trichloroethylene; Aliphatic cyclic ether compounds such as tetrahydrofuran and dioxane; Ketone compounds such as methyl ethyl ketone and cyclohexanone; Ethyl acetate and dimethyl Examples include ester compounds such as phthalate, methyl salicylate, and amyl acetate; alcohols such as n-butanol, ethanol, and iso-butanol; and 1-nitropropane, carbon disulfide, and limonene. These solvents can be used as a mixture as required.
  • Examples of the resin according to the present invention include 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, gravure printing, flexographic printing. , Screen printing, ink jet printing, letterpress reversal printing, and the like. Note that since the insulating film of the present invention is formed using these methods, the insulating film of the present invention is required to have excellent solubility in general-purpose solvents.
  • the resin according to the present invention When the resin according to the present invention is used as an insulating film, it can be used in a state where the film is formed or as a cross-linked product that is photo-crosslinked (photocyclized) as necessary.
  • the general-purpose solvent used for forming the film exhibits good solubility, and the upper portion of the film
  • the organic semiconductor layer can be formed using a solvent different from the general-purpose solvent.
  • the film has solvent resistance (crack resistance) with respect to the organic semiconductor solution, it can be used as an insulating film with the film formed.
  • it is not excellent in solvent resistance (crack resistance) film formation by a printing method cannot be performed, and it is necessary to form into a film by methods, such as a vapor deposition method inferior to the printing method.
  • UV rays having a wavelength of 245 to 350 nm are exemplified.
  • the irradiation amount is appropriately changed depending on the composition of the resin. For example, 150 to 3000 mJ / cm 2 can be mentioned, and it is preferable to prevent a decrease in the degree of crosslinking and to improve economy by shortening the process. 50 to 1000 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, anthracene compounds, anthraquinone compounds, thioxanthone compounds, nitrophenyl compounds, etc., but benzophenone compounds having high compatibility with the resin used in the present invention. Is preferred.
  • the sensitizers can be used in combination of two or more as required.
  • the resin of the present invention can be crosslinked by ultraviolet rays, but may be heated if necessary.
  • the temperature in the case of heating in addition to the ultraviolet irradiation is not particularly limited, but a temperature of 120 ° C. or lower is preferable in order to avoid thermal deformation of the resin used.
  • the resin of the present invention can be crosslinked efficiently in a short time, and the time required for crosslinking can be within 5 minutes. Note that, since it is suitable for controlling the crosslinking time, the time required for crosslinking is preferably within 1 to 2 minutes.
  • the resin of the present invention can be formed into a film and used as a gate insulating layer (polymer dielectric layer) in an organic field effect transistor (OFET).
  • the organic field effect transistor can be obtained, for example, by laminating an organic semiconductor layer provided with a source electrode and a drain electrode and a gate electrode on a substrate via a gate insulating layer (polymer dielectric layer). .
  • the insulating film obtained from the resin of the present invention has a low leakage current because the formation of fine holes (pinholes) that cause leakage is suppressed. Further, when the insulating film is used as a polymer dielectric layer, the leakage current is preferably 0.01 nA or less from the viewpoint of practicality as an organic field effect transistor (OFET) element.
  • OFET organic field effect transistor
  • the insulating film obtained from the resin of the present invention has excellent wettability with respect to a solvent.
  • a gate insulating layer polymer dielectric layer
  • the bottom gate / bottom contact (BGBC) type and the top gate / bottom contact are used.
  • BGBC bottom gate / bottom contact
  • TGBC TGBC type organic field effect transistor device
  • the insulating film obtained from the resin of the present invention has excellent flatness.
  • the surface roughness (Ra) is 0. 0 from the viewpoint of flatness. It is preferable that it is 5 nm or less.
  • the threshold voltage of the FET element is 0 from the viewpoint of practicality as an organic field effect transistor (OFET) element. It is preferably 2.0 V or less, or ⁇ 2.0 V or more and less than 0 V.
  • the mobility of the FET element is 0. 0 from the viewpoint of practicality as an organic field effect transistor (OFET) element. It is preferably 20 cm 2 / Vs or more.
  • the on-current / off-current of the FET element is preferably 10 6 or more.
  • the insulating film obtained from the resin of the present invention is used as a gate insulating layer (polymer dielectric layer), from the viewpoint of practicality as an organic field effect transistor (OFET) element, the source-drain current of the FET element It is preferable that there is no hysteresis.
  • the dielectric breakdown strength of the FET element is 4 MV from the viewpoint of practicality as an organic field effect transistor (OFET) element. / Cm or more is preferable.
  • the organic field effect transistor is a bottom gate / bottom contact (BGBC) type, a bottom gate / top contact (BGTC) type, a top gate / bottom contact (TGBC) type, a top gate / top contact (TGTC).
  • BGBC bottom gate / bottom contact
  • TGBC top gate / bottom contact
  • TGTC top gate / top contact
  • the resin of the present invention is suitably used as a planarizing film containing the resin of the present invention and / or a cross-linked product of the resin of the present invention, and is particularly suitably used as an insulating planarizing film capable of continuous printing.
  • the planarizing film is a film made of an insulating resin that is applied on the base material and used for the purpose of reducing the surface roughness of the base material itself.
  • the planarizing film obtained from the resin of the present invention can be continuously printed by dissolving in the above-mentioned organic solvent, has excellent insulating properties and flatness, and can be particularly suitably used as a repellent patterning film.
  • the hydrophilic / repellent patterning is a technique of patterning by hydrophilicizing the surface of a plastic using vacuum ultraviolet (VUV), and a film having a surface patterned by using the technique is called a hydrophilic / repellent patterning film. is there.
  • the new repellent patterning film of the present invention is also preferable in that it can prevent the occurrence of defects when the aqueous metal nano ink is applied.
  • the hydrophilic / repellent patterning is preferably performed by irradiating vacuum / ultraviolet pattern (VUV) having a wavelength of 10 nm to 200 nm to the hydrophilic / repellent patterning film through a photomask having a chromium pattern.
  • VUV vacuum / ultraviolet pattern
  • the distance between the light source and the film and the distance between the mask and the film are appropriately selected depending on the composition of the hydrophilic / repellent patterning film to be used.
  • VUV vacuum / ultraviolet pattern
  • it can be performed under a gas having various compositions ranging from the atmosphere to nitrogen.
  • the irradiation time of VUV is not limited as long as good repellent patterning can be performed, but it is more suitable for preventing film deterioration and more suitable for receptive patterning. A range is preferable.
  • a hydrophilic pattern is drawn on the hydrophobic film by the hydrophilic / repellent patterning.
  • the contact angles of the hydrophobic region and the hydrophilic region with respect to water are preferably 100 ° or more and 20 ° or less, respectively.
  • the difference in contact angle is preferably 80 ° or more.
  • the surface tension difference between the hydrophobic region and the hydrophilic region is preferably 40 mN / m.
  • the drying temperature and the baking temperature are not limited as long as the substrate and the hydrophilic / repellent patterning film are not affected.
  • the drying temperature is preferably 10 to 50 ° C.
  • the heating and baking temperature is preferably 100 to 180 ° C. It is done.
  • resolution in the hydrophobic / repellent patterning film is appropriately selected depending on the application, but is preferably 10 ⁇ m or less from the viewpoint of practicality.
  • “resolution” refers to a pattern in which a linear electrode wiring (line) having a width of A micron is optically patterned using a mask in which A micron intervals (spaces) are arranged at equal intervals, and then metal When wiring is formed with nano ink, it means the minimum value of A that can form wiring with the shape of a mask. In this case, the line and space is A micron resolution.
  • the metal nanoink that can be used in the present invention and the concentration of metal nanoparticles contained in the ink are not limited as long as a low-resistance metal wiring can be formed.
  • examples include inks containing metal nanoparticles such as gold, silver, platinum, etc., and solids concentrations of, for example, 5 to 50 wt% can be mentioned.
  • an ink using water or a water / alcohol mixed solvent is exemplified as a medium for dispersing the metal nanoparticles.
  • the type of alcohol is not limited as long as it is compatible with water, and examples thereof include methanol and ethanol.
  • the threshold value of the FET element is used from the viewpoint of practicality as an organic field effect transistor (OFET) element including the electrode
  • the voltage is preferably more than 0 and not more than 2.0V, or more than ⁇ 8.0V and less than 0V, more preferably more than 0 and less than 2.0V, or more than ⁇ 2.0V and less than 0V.
  • the FET element is moved from the viewpoint of practicality as an organic field effect transistor (OFET) element including the electrode.
  • the degree is preferably 0.20 cm 2 / Vs or more.
  • the FET element is turned on from the viewpoint of practicality as an organic field effect transistor (OFET) element including the electrode.
  • the current / off-current ratio is preferably 10 6 or more.
  • the source of the FET element -It is preferable that there is no hysteresis of current between drains.
  • a substrate that can be used is not particularly limited as long as sufficient flatness capable of producing an element can be secured.
  • a multilayered material may be used.
  • the surface of these materials can also be coated.
  • 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.
  • Examples of the conductive gate electrode, source electrode, or drain electrode that can be used in the present invention include gold, silver, aluminum, copper, titanium, platinum, chromium, polysilicon, silicide, indium / tin / oxide (ITO), A conductive material such as tin oxide is exemplified. In addition, a plurality of these conductive materials can be stacked.
  • the electrode formation method is not particularly limited, and examples thereof include vapor deposition, high-frequency sputtering, electron beam sputtering, and the like.
  • vapor deposition high-frequency sputtering, electron beam sputtering, and the like.
  • solution spin coating drop Methods such as casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, ink jet printing, letterpress reverse printing and the like can also be employed.
  • 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 can be used as a bipolar transistor that combines N-type and P-type. Examples are (F-1) to (F-10).
  • both low-molecular and high-molecular organic semiconductors can be used, and these can be used in combination.
  • 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. There is no limitation as long as it can be formed.
  • the 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. Therefore, the content 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.
  • Suitable solvents are those having a high boiling point and a boiling point of 100 ° C. or higher, xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, decahydro- 2-Naphthol is preferred.
  • the mixed solvent which mixed 2 or more types of the above-mentioned solvent in the appropriate ratio 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.
  • solubility in general-purpose solvents crosslinking temperature, time required for crosslinking, solvent resistance (crack resistance), dielectric breakdown strength, leakage current, wettability to solvent, and flatness in the case of a film
  • a resin suitable for a polymer dielectric layer having excellent performance can be provided.
  • FIG. 2 is a diagram showing a cross-sectional shape of a bottom gate-bottom contact (BGBC) type element.
  • FIG. 2 is a view showing a 1 H-NMR chart of Resin 1 produced in Example 1. The hysteresis between the source-drain current (I SD ) (solid line) observed when the gate voltage (V GS ) is changed in the OFET device manufactured in Example 1 is not observed, and the leakage current value (I L ) (Broken line) is a figure showing that it is as small as 0.01 nA or less.
  • FIG. 2 is a view showing a cross-sectional shape of a top gate / bottom contact (TGBC) type element;
  • FIG. 10 is a view showing a test pattern of an Ag wiring formed by repellent patterning in Example 9.
  • the organic semiconductor (di-n-hexyldithienobenzodithiophene) used in the examples was synthesized according to the production method described in JP-A-2015-224238.
  • 2-oxo-2H-1-benzopyran-6-carbonyl chloride (the following formula (G)) is 4- [2- (4-pyridinyl) ethenyl] benzoyl chloride (formula (G)) according to CN 103183634.
  • the following formula (H)) was synthesized in accordance with the method described in Journard-Fur Practice Hemi, Vol.
  • NMR NMR
  • spin coating film thickness measurement
  • dispenser printing UV irradiation, vacuum deposition, UV irradiation amount necessary for crosslinking
  • wettability of polymer dielectric layer to solvent dielectric breakdown strength
  • OFET element The solvent resistance (crack resistance) was evaluated under the following conditions and equipment.
  • ⁇ NMR> Measurement was performed using JNM-ECZ400S FT-NMR (manufactured by JEOL Ltd.).
  • the mole fraction X of the photocyclization group in the aromatic group can be obtained by the following formula using the integrated intensity of the peak obtained by 1 H-NMR measurement.
  • ⁇ Dispenser printing> An IMAGE MASTER 350PC SMART manufactured by Musashi Engineering Co., Ltd. was used.
  • ⁇ UV irradiation> Using UV-System and CSN-40A-2 manufactured by GS Yuasa Corporation, the UV irradiation time was adjusted by changing the transport speed under the condition of UV intensity of 4.0 kW.
  • ⁇ Vacuum deposition> A small vacuum deposition apparatus VTR-350M / ERH manufactured by ULVAC KIKOH Co., Ltd. was used.
  • solvents toluene, tetralin, xylene, mesitylene, chlorobenzene
  • the organic semiconductor solution covering the S electrode and the D electrode it is possible to cover all over the electrode if the shape at the moment when the droplet is applied is maintained or if it spreads wet. It was evaluated as (1 point).
  • the droplet contracts and / or moves the electrode cannot be covered, and thus the case where the liquid contracts and / or moves is evaluated as defective (0 point).
  • the score is 5 when good results are obtained with all solvents.
  • a bottom gate / bottom contact (BGBC) type element which is one form of an organic field effect transistor, is manufactured, and the gate voltage is changed by using a semiconductor parameter analyzer SCS4200 manufactured by Keithley, with a source-drain voltage of minus 60 volts.
  • SCS4200 semiconductor parameter analyzer manufactured by Keithley
  • Parylene dimer was introduced into PDS2010 manufactured by Japan Parylene LLC and a film was formed by chemical vapor deposition.
  • the surface of the planarizing film was patterned into a lyophilic portion and a lyophobic portion by irradiating with vacuum ultraviolet rays (VUV) through a photomask having a chromium pattern with a line and space of 5 to 50 microns.
  • VUV vacuum ultraviolet rays
  • This substrate is placed in an automatic film applicator body heated to 70 ° C., and after dropping Ag nano ink, the film applicator with film thickness adjusting function is moved at a speed of 140 mm / s, coating is performed, and baking is performed at 120 ° C. for 30 minutes. did. All the formed patterns were observed, and the smallest line and space value among the patterns formed without defects was defined as the resolution.
  • Example 1 ⁇ Resin synthesis>
  • a 300 mL Schlenk tube was charged with 5.0 g of polystyrene having a weight average molecular weight of 280,000 (hereinafter referred to as “raw polymer A”), 150 mL of dehydrated methylene chloride, and 4.0 g of cinnamic acid chloride. Dissolved. 9.0 g of trifluoromethanesulfonic acid (hereinafter referred to as “TFMS”) was charged into a 30 mL dropping funnel having a three-way cock attached to the upper portion and the lower portion sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed.
  • TFMS trifluoromethanesulfonic acid
  • the reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 ⁇ m Teflon (registered trademark) filter, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice, followed by drying at 50 ° C. under reduced pressure to obtain 6.8 g. Of resin 1 was obtained.
  • Teflon registered trademark
  • a toluene solution (3 wt%) of the obtained resin 1 was spin-coated on the substrate on which the electrode was formed under the conditions of 500 rpm ⁇ 5 seconds and 1000 rpm ⁇ 20 seconds, and dried at 50 ° C. for 5 minutes (insulation) Formation of Film)
  • a polymer dielectric layer having a thickness of 520 nm was formed by irradiation with 250 mJ / cm 2 of ultraviolet rays.
  • 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 a channel width of 500 ⁇ m.
  • Example 2 In a nitrogen box, a 300 mL Schlenk tube was charged with 10 g of the starting polymer A, 260 mL of dehydrated methylene chloride, and 19.2 g of cinnamic acid chloride, and dissolved under stirring at room temperature. 26 g of TFMS was charged into a 100 mL dropping funnel with a three-way cock attached to the top and the bottom sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed. 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 TFMS 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 55 hours.
  • the reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 36 g of saturated sodium bicarbonate was dissolved was added to neutralize TFMS and hydrochloric acid in the system.
  • the reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer.
  • the obtained resin 2 (the following formula) has 30 mol% and 70 mol% of the structural units represented by formula (1) and formula (2), respectively. confirmed.
  • Example 3 Resin 3 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to coumarin-6-carboxylic acid chloride.
  • the obtained resin 3 (the following formula) has 75 mol% and 25 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.
  • Example 4 Resin 4 was obtained in the same manner as in Example 1, except that cinnamic acid chloride was changed to coumarin-6-carboxylic acid chloride.
  • Example 5 Resin 5 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to pyridinylethenyl benzoic acid chloride.
  • Example 6 As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
  • Resin 6 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to pyridinylethenylbenzoic acid chloride.
  • the obtained resin 6 (the following formula) has 58 mol% and 42 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.
  • Example 7 As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
  • Example 7 Resin 7 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to phenylethenylbenzoic acid chloride.
  • the obtained resin 7 (the following formula) has 60 mol% and 40 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.
  • Example 8 As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance.
  • Resin 8 was obtained in the same manner as in Example 1 except that cinnamic acid chloride was changed to phenylethenylbenzoic acid chloride.
  • the obtained resin 8 (the following formula) has 40 mol% and 60 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.
  • Example 9 Polystyrene-b-poly (ethylene propylene) -b-polystyrene (SEPS) having a weight average molecular weight of 150,000 and a polystyrene content of 65 wt% in a 300 mL Schlenk tube in a nitrogen box (hereinafter referred to as “raw polymer B”) 4 .01 g, 150 mL of dehydrated methylene chloride, and 4.5 g of cinnamic acid chloride were charged and dissolved under stirring at room temperature. Next, the Schlenk tube was cooled to 0 ° C.
  • SEPS Polystyrene-b-poly (ethylene propylene) -b-polystyrene
  • the obtained resin 9 (the following formula) has 27 mol% and 29 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.
  • the xylene solution (3 wt%) of the resin 9 obtained was spin-coated on the cleaned and dried 30 ⁇ 30 mm 2 glass (base material) (Eagle XG manufactured by Corning) under the conditions of 500 rpm ⁇ 5 seconds and 1500 rpm ⁇ 20 seconds. After drying at 50 ° C. for 5 minutes, an undercoat film having a thickness of 100 nm was formed by irradiation with ultraviolet rays of 100 mJ / cm 2 . Then, VUV was irradiated for 180 seconds through the photomask, and the surface of the base film was patterned to be lyophilic and liquid repellent.
  • This substrate is placed on an automatic film applicator body heated to 70 ° C., and after Ag nanoink is dropped, the film applicator with a film thickness adjusting function is applied at a speed of 140 mm / s, coating is performed, and baking is performed at 120 ° C. for 30 minutes.
  • a source electrode and a drain electrode having a thickness of 500 nm, a channel length of 5 ⁇ m, a channel width of 500 ⁇ m, and an electrode width of 100 ⁇ m were formed. Thereafter, it was immediately immersed in an isopropanol solution of pentafluorobenzenethiol 30 mmol / L, taken out after 5 minutes, washed with isopropanol, and blow-dried.
  • a 0.8 wt% xylene / tetralin mixed solution of an organic semiconductor (di-n-hexyldithienobenzothiophene) was formed by spin coating. In order to volatilize the solvent, it was dried at 90 ° C. for 20 minutes. Thereafter, 0.6 g of the obtained substrate and parylene dimer are placed in a vacuum vapor deposition device, heated in vacuum to vaporize the parylene dimer, polymerized on the substrate, and gate insulation composed of polyparaxylylene having a thickness of 430 nm. Layers were deposited.
  • VUV was irradiated for 180 seconds through a photomask, and the surface of the gate insulating film was patterned to be lyophilic and lyophobic.
  • This substrate is placed in an automatic film applicator body heated to 70 ° C, and after dropping Ag nano ink, it is applied at a rate of 140 mm / s and baked at 90 ° C for 20 minutes to form a gate electrode having a thickness of 500 nm.
  • a top gate / bottom contact (TGBC) type organic field effect transistor device was fabricated. The structure of the produced organic field effect transistor is shown in FIG.
  • Example 10 In a nitrogen box, a 300 mL Schlenk tube was charged with 4.01 g of the raw material polymer B, 150 mL of dehydrated methylene chloride, and 5.99 g of cinnamic acid chloride, and dissolved at room temperature with stirring. Next, the Schlenk tube was cooled to 0 ° C. or lower, and 8.2 g of TFMS was dropped using a syringe. The color of the polymer solution colored reddish purple as it was dropped. After completion of dropping, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 25 hours.
  • the reaction solution was cooled again with ice water, and then a saturated aqueous solution in which 9.14 g of saturated sodium bicarbonate was dissolved was added to neutralize TFMS and hydrochloric acid in the system.
  • the reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer.
  • This solution was filtered through a 3 ⁇ m Teflon (registered trademark) filter. Subsequently, the filtrate was passed through a silica gel column to remove impurities and decolorized, and then reprecipitated with 1.5 L of methanol. Further, the polymer was purified by reprecipitation and dried under reduced pressure at 40 ° C. to obtain 6.0 g of resin 10.
  • the obtained resin 10 (the following formula) has 21 mol% and 32 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.
  • Example 11 In a nitrogen box, a 300 mL Schlenk tube was charged with 3.0 g of raw material polymer B, 150 mL of dehydrated methylene chloride, and 6.3 g of cinnamic acid chloride, and dissolved at room temperature with stirring. Next, the Schlenk tube was cooled to 0 ° C. or lower, and 8.44 g of TFMS was added dropwise using a syringe. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed at room temperature for 29 hours.
  • the obtained resin 11 (the following formula) has 17 mol% and 39 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.
  • Example 12 In a nitrogen box, a 300 mL Schlenk tube was charged with 10 g of the starting polymer A, 260 mL of dehydrated methylene chloride, and 19.2 g of cinnamic acid chloride, and dissolved under stirring at room temperature. 26 g of TFMS was charged into a 100 mL dropping funnel with a three-way cock attached to the top and the bottom sealed. The Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed.
  • 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. Next, it cooled in the low temperature thermostat, and TFMS was dripped over 10 minutes from the dropping funnel, stirring with a magnetic stirrer. The color of the polymer solution colored reddish purple as it was dropped. After completion of dropping, the reaction was carried out at 1 ° C. for 55 hours. Of 360 mL of saturated aqueous solution in which 36 g of saturated sodium bicarbonate was dissolved, 100 mL was slowly added dropwise. The remaining saturated sodium bicarbonate solution was placed in a 1 L beaker, and 100 g of ice was added and cooled.
  • reaction solution was poured into this beaker and stirred for 2 hours, and then transferred to a separatory funnel to separate the methylene chloride layer. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer.
  • the polymer solution was reprecipitated with 3 L of methanol twice, filtered and dried under reduced pressure at 50 ° C. to obtain 17.9 g of resin 12.
  • the obtained resin 12 (the following formula) was obtained by converting the structural units represented by the formula (1), the formula (2) and the formula (18) to 36.5 mol% and 62.5 It was confirmed that they had mol% and 1.0 mol%.
  • Example 13 In a nitrogen box, a 300 mL Schlenk tube was charged with 1.1 g of the raw material polymer B, 30 mL of dehydrated methylene chloride and 1.3 g of 3- (perfluorohexyl) propionyl chloride, and dissolved at room temperature with stirring. Next, the Schlenk tube was cooled with ice water, and 1.2 g of TFMS was added dropwise using a syringe under a nitrogen flow. The color of the polymer solution colored reddish purple as it was dropped. After completion of the dropwise addition, the ice-water bath was removed and the reaction was allowed to proceed for 48 hours at room temperature.
  • reaction solution was cooled again with ice water, and then an aqueous solution in which 1.2 g of sodium bicarbonate was dissolved was added dropwise to neutralize TFMS and hydrochloric acid in the system.
  • the reaction solution was transferred to a separatory funnel and the aqueous phase was separated. Further, the methylene chloride phase was washed with water three times and separated to obtain a methylene chloride solution of the polymer.
  • This solution was reprecipitated with 300 mL of methanol. Further, the polymer was purified by reprecipitation twice and dried under reduced pressure at 40 ° C. to obtain 1.7 g of resin 13-a (the following formula).
  • reaction solution was cooled again with ice water, and then an aqueous solution in which 1.2 g of sodium bicarbonate was dissolved was added dropwise to neutralize TFMS and hydrochloric acid in the system.
  • the reaction solution was transferred to a separatory funnel and the aqueous phase was separated. Further, the methylene chloride phase was washed with water three times and separated to obtain a methylene chloride solution of the polymer.
  • This solution was reprecipitated with 350 mL of methanol. Furthermore, the polymer was purified by reprecipitation twice and dried under reduced pressure at 40 ° C. to obtain 1.1 g of resin 13.
  • the obtained resin 13 (the following formula) was obtained by adding 3 mol%, 29 mol%, and 29 mol% of structural units represented by formula (1), formula (2), and formula (19), respectively. And 24 mol%.
  • Example 1 As in Example 1, it was confirmed that the organic field effect transistor device had excellent performance. ⁇ Evaluation of repellent patterning performance> Evaluation was made in the same manner as in Example 9, and it was confirmed that good drawing was achieved with all the lines and spaces of 5 to 50 microns, and that there was a resolution of 5 microns. The obtained film had a surface roughness of 0.3 nm and excellent flatness.
  • Comparative Example 1 In a nitrogen box, a 300 mL Schlenk tube was charged with 5.0 g of the starting polymer A, 150 mL of dehydrated methylene chloride, and 3.9 g of anhydrous aluminum chloride, and dissolved at room temperature with stirring.
  • a 30-mL dropping funnel with a three-way cock attached to the upper part and a sealed lower part was charged with 30 mL of methylene chloride solution of 4.0 g of cinnamic acid chloride.
  • the Schlenk tube and the dropping funnel were taken out from the nitrogen box, and the Schlenk tube and the dropping funnel were connected with nitrogen sealed.
  • 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 obtained resin 14 (the following formula) has 86 mol% and 14 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.
  • 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 then a saturated aqueous solution in which 2.1 g of saturated sodium bicarbonate was dissolved was added to neutralize hydrochloric acid in the system.
  • the reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 ⁇ m Teflon (registered trademark) filter, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice, followed by drying at 50 ° C. under reduced pressure to 4.7 g Of resin 15 was obtained.
  • Teflon registered trademark
  • the obtained resin 15 (the following formula) has 92 mol% and 8 mol% of the structural units represented by the formulas (1) and (2), respectively. confirmed.
  • 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 9 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 then a saturated aqueous solution in which 3.9 g of saturated sodium bicarbonate was dissolved was added to neutralize hydrochloric acid in the system.
  • the reaction was transferred to a separatory funnel and the methylene chloride layer was separated. Further, the aqueous layer was washed with methylene chloride three times and separated to obtain a methylene chloride solution of the polymer. This solution was filtered through a 3 ⁇ m Teflon (registered trademark) filter, reprecipitated with 1.5 L of methanol, and the polymer was isolated by filtration twice, followed by drying at 50 ° C. under reduced pressure to obtain 4.9 g. Of resin 16 was obtained.
  • Teflon registered trademark
  • the obtained resin 16 (the following formula) has 87 mol% and 13 mol% of the structural units represented by formula (1) and formula (2), respectively. confirmed.
  • the obtained resin 20 (the following formula) has 86 mol% and 14 mol% of structural units represented by formula (1) and formula (2), respectively. confirmed.
  • the obtained resin 22 (the following formula) has 85 mol% and 15 mol% of the structural units represented by the formulas (1) and (2), respectively. It was confirmed.

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  • Thin Film Transistor (AREA)

Abstract

L'invention fournit une résine qui présente d'excellentes performances du point de vue de la solubilité dans des solvants d'usage général, de la température de réticulation, de la durée nécessaire à la réticulation, de la résistance aux solvants (résistance aux fissures), de la rupture diélectrique, du courant de fuite, de la mouillabilité vis-à-vis d'un solvant, et de la planéité dans le cas d'une transformation en film mince. La résine de l'invention contient des unités de répétition représentées par les formules (1) et (2), et plus précisément contient 20% en moles ou plus de l'unité de répétition de la formule (2) par rapport au nombre total des unités de répétition des formules (1) et (2). (Dans la formule (1), Ｒ１ représente un hydrogène ou un groupe alkyle en C1 à C6, S1 représente －Ｏ－ ou －Ｃ（Ｏ）－, p représente 0 ou 1, Ａ１ représente un groupe aryle en C6 à C19, et Y représente un halogène, un groupe cyano, un groupe carboxyalkyle, un groupe alkyléther, un groupe aryléther, un groupe alkyle en C1 à C18, un groupe fluoroalkyle, ou un groupe cycloalkyle. En outre, k représente un entier de 0 à (s-1), s représentant le nombre d'atomes de carbone configurant un groupe aromatique Ａ1.) {Dans la formule (2), Ｒ２ représente un hydrogène ou un groupe alkyle en C1 à C6, Ｓ２ représente －Ｏ－ ou －Ｃ（Ｏ）－, q représente 0 ou 1, Ａ２ représente un groupe aryle en C6 à C19, Y représente un substituant défini par la formule (1), j représente un entier de 0 à (r-2), et m représente un entier de 1 à (r-j-1), r représentant le nombre d'atomes de carbone configurant un groupe aromatique Ａ２. En outre, Z représentent au moins un groupe organique choisi parmi (A) à (D).) (Dans les formules (A) à (D), Ｒ３ et Ｒ４ représentent chacun indépendamment un hydrogène, un groupe alkyle en C1 à C6, un groupe aryle, ou un groupe carboxyalkyle. Ｒ５ à Ｒ２９ représentent chacun indépendamment, un hydrogène, un halogène, un groupe cyano, un groupe carboxyalkyle, un groupe alkyléther, un groupe aryléther, un groupe alkyle en C1 à C18, un groupe fluoroalkyle, ou un groupe cycloalkyle.)}
PCT/JP2018/009167 2017-03-16 2018-03-09 Polymère photoréticulable, film isolant, film aplati, et film à motif d'attraction/répulsion ainsi que dispositif de transistor organique à effet de champ contenant celui-ci Ceased WO2018168676A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/494,107 US12291587B2 (en) 2017-03-16 2018-03-09 Photocrosslinkable polymer, insulating film, planarization film, lyophilic/liquid repellent patterned film, and organic field effect transistor device comprising same
EP18767508.7A EP3597673B1 (fr) 2017-03-16 2018-03-09 Polymère photoréticulable, film isolant, film aplati, et film à motif d'attraction/répulsion ainsi que dispositif de transistor organique à effet de champ contenant celui-ci
CN201880017891.8A CN110418808B (zh) 2017-03-16 2018-03-09 光交联性聚合物、绝缘膜、平坦化膜、亲疏图案化膜和包含其的有机场效应晶体管器件

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JP2017051670 2017-03-16
JP2017-051670 2017-03-16
JP2017199489A JP6953986B2 (ja) 2017-10-13 2017-10-13 光架橋性重合体、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
JP2017-199489 2017-10-13
JP2018-011579 2018-01-26
JP2018011579A JP6992545B2 (ja) 2018-01-26 2018-01-26 光架橋性重合体、絶縁膜、親撥パターニング膜およびこれを含む有機トランジスタ
JP2018011580A JP6992546B2 (ja) 2017-03-16 2018-01-26 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
JP2018-011580 2018-01-26

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JP7480484B2 (ja) 2019-09-26 2024-05-10 東ソー株式会社 樹脂組成物

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