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WO2011004938A1 - Matériau isolant de polyimide durcissable à basse température obtenu à partir d'une composition de résine d'acide polyamique ayant une structure de tassement élevée, et dispositif transistor à couches minces tout organique ayant de faibles propriétés d'hystérésis conférées par la composition - Google Patents

Matériau isolant de polyimide durcissable à basse température obtenu à partir d'une composition de résine d'acide polyamique ayant une structure de tassement élevée, et dispositif transistor à couches minces tout organique ayant de faibles propriétés d'hystérésis conférées par la composition Download PDF

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WO2011004938A1
WO2011004938A1 PCT/KR2009/005694 KR2009005694W WO2011004938A1 WO 2011004938 A1 WO2011004938 A1 WO 2011004938A1 KR 2009005694 W KR2009005694 W KR 2009005694W WO 2011004938 A1 WO2011004938 A1 WO 2011004938A1
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polyimide resin
thin film
low temperature
polyimide
polyamic acid
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Korean (ko)
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이미혜
안택
최유정
정현민
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Korea Research Institute of Chemical Technology KRICT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials

Definitions

  • the present invention relates to a high-packing structure polyimide insulating film prepared by imidation of a polyamic acid under an amino alcohol compound catalyst useful as an imidization reaction catalyst, and to an all-organic thin film transistor device using the same, and more particularly to aromatic tetracarboxylic acid dianhydride
  • an organic catalyst capable of low temperature curing is contained as an essential composition, and a low temperature imidization reaction in a range of 100 to 200 ° C is possible.
  • the present invention relates to a novel low-temperature-curable polyamic acid resin composition to which a high packing structure is applied, and to an all-organic thin film transistor device manufactured therefrom.
  • the imidation reaction carried out under the low temperature hardening catalyst according to the present invention is smoothly performed at a low temperature of 100 ° C. to 200 ° C. as well as at a high temperature of 200 ° C. or higher, which is a general imidization reaction temperature, and also dramatically reduces the amount of catalyst remaining in the produced polyimide. It lowers and the effect which provides the all-organic thin film transistor element excellent in time stability is acquired.
  • the polyimide resin is a high heat resistant resin prepared by imidating an aromatic tetracarboxylic acid or a derivative thereof and an aromatic diamine or an aromatic diisocyanate, and may have various molecular structures depending on the type of monomer used.
  • polyimide resins are insoluble and insoluble ultra-high heat resistant resins, which have the following characteristics: (1) excellent thermal oxidation resistance, and (2) a very high usable temperature, a long service life of about 260 ° C, and short-term use. Temperature is very good at around 480 °C, (3) excellent electrochemical and mechanical properties, (4) good radiation and low temperature properties, (5) intrinsic flame retardancy, (6) good chemical resistance.
  • polyimide is synthesized by using a polyamic acid obtained by condensing aromatic tetracarboxylic dianhydride and aromatic diamine in an solvent as an amide group linkage, by heating and dehydrating it to form an imide ring, or chemically using a dehydrating agent. It synthesize
  • Polyimide generally has its glass transition temperature of 350 ° C or higher, and due to its inherent property, once polyimide is formed from polyamic acid by imidization, it is difficult to be formed by heating above the glass transition temperature. Since the physical properties are lowered by the resin, a resin is obtained in the necessary properties such as a film when forming a polyimide from the polyamic acid.
  • the method of forming a polyimide from the polyamic acid through dehydration and cyclization by a heating method generally requires a high temperature of 300 ° C to 400 ° C and is difficult to form after polyimide formation to form a polyimide thin film or film. It will be imidized on the part material.
  • the limitation of the production temperature is limited to the energy consumption or the design of the manufacturing apparatus, but when the polyimide forming site is not suitable for a high temperature process, the formation of the polyimide itself becomes difficult.
  • a method of forming a polyimide through dehydration cyclization by chemical method using a dehydrating agent enables the formation of polyimide even at a low temperature of 200 ° C. or less, but by using at least one equivalent of dehydrating agent, more than equivalent equivalent of dehydration by-product is produced and completed.
  • Polyimide formed by the imidization is not disadvantageous that the physical properties are poor.
  • a method of forming a polyimide by performing imidization under conditions using a catalyst such as an acid or a base with a dehydrating agent has been known.
  • a catalyst such as an acid or a base with a dehydrating agent
  • an imidation was carried out at a low temperature of 200 ° C. or lower using an organic acid such as p -hydroxyphenylacetic acid or the like to obtain a polyimide [M. Oba, J. Polym. Science: Part A: Polymer Chemistry , 1996, 34 , 651-658.
  • the present inventors have completed the low-temperature imidization reaction by identifying an imidization reaction mechanism and developing a novel catalyst effective to reduce the activation energy required for the dehydration reaction, which is a reaction rate determining step, and applied it as an insulating material of a thin film transistor element.
  • inorganic thin films having a high dielectric constant such as silicon nitride, barium strontium, and barium titanate are generally used.
  • a disadvantage that expensive vacuum equipment is required for deposition.
  • U.S. Patent No. 5,946,551 et al. Reported the result of forming an inorganic thin film from a precursor of an inorganic thin film by a chemical solution process at a relatively low temperature. In this case, however, a process temperature of about 300 to 700 ° C. is required.
  • the low temperature thinning process on plastic substrates such as polycarbonate, polysulfone, polyethersulfone, which are limited to 200 ° C. or less, has a difficult disadvantage.
  • the inventors of the present invention polymerized a mixture of 1 aromatic diamine mixture and 2 a specific aromatic tetracarboxylic dianhydride to prepare a polyamic acid resin, and at a temperature in the range of 100 ⁇ 200 °C
  • the polyimide resin prepared after the addition of the catalyst mixture showing the high degree of imidization shows not only a high degree of imidization of more than 95%, but also excellent thin film characteristics, so that the organic transistor device manufactured therefrom has a low off-current and high electric field.
  • the present invention has been completed by confirming excellent device characteristics such as effective charge mobility, low hysteresis characteristics, and excellent aging stability.
  • the polyimide resin can be processed at a low temperature of 100 to 200 ° C. while maintaining almost all the characteristics of the existing polyimide resin, and the thin film transistor prepared therefrom has low off-current, high field effect charge mobility, and low It offers features that possess hysteresis and excellent time stability.
  • an object of the present invention is to provide a low-temperature-curable polyimide resin having excellent physical properties as an advanced industrial core material such as an organic thin film transistor and a thin film transistor element in which they are introduced as an insulator.
  • This invention solves the said subject by providing the amino alcohol compound represented by following formula (2) as a catalyst for imidation reaction.
  • R One , R 2 , R 3 , And R 4 Represents a hydrogen atom, a C1-C12 alkyl group, or a C1-C12 hydroxyalkyl group, respectively, n is an integer of 0-4.
  • the present invention solves the above problems by providing a method for producing a polyimide resin using an aminoalcohol compound represented by the formula (2) as a catalyst in a method for producing a polyimide by imidating a polyamic acid in the presence of a catalyst. .
  • the catalyst of the present invention achieves the effect of promoting the imidization reaction even at low temperature of less than 200 ° C by lowering the activation energy required in the process of forming the imide ring from the amic acid group.
  • the catalyst of the present invention has an effect of producing a high molecular weight and high purity polyimide by suppressing a reverse reaction in which polyamic acid is converted into an acid anhydride and diamine.
  • the catalyst of the present invention has a low boiling point and is easily removed after the imidization reaction, the catalyst has an effect of solving the problem of remaining in the polyimide.
  • the polyimide produced using the catalyst of the present invention is not known exactly why, but provides a very excellent polyimide resin having high field effect charge mobility, low hysteresis and little change with time, and according to the present invention
  • the organic thin film transistor device using the manufactured polyimide also provides a device having excellent characteristics intact the above characteristics.
  • the organic thin film transistor device using the polyimide of the present invention preferably has a field effect charge mobility of 1.0 cm 2 / Vs or more, a hysteresis of 1.5 or less, and a time-dependent change of 20% or less based on a hysteresis change after 30 days. Very good properties.
  • the polyimide resin produced by using the catalyst of the present invention in the polyamic acid used in the present invention is a polyamic acid represented by the following formula (1) and a polyimide prepared therefrom.
  • n is a natural number ranging from 10 to 1000;
  • R 11 is each an alkyl or aryl group having 1 to 30 carbon atoms;
  • Y is one selected from an ester group, an amide group, an imide group, and an ether group.
  • the polyimide resin of the present invention preferably has an intrinsic viscosity of 1.0 to 3.0 g / dL, a weight average molecular weight of 10,000 to 500,000 g / mol, a dielectric constant of 2 to 6 and a surface tension of 30 to It is a low-temperature-curable polyimide resin of 65 dyne / cm in the present invention is prepared by thermal curing at low temperature for 60 to 120 minutes at 100 ⁇ 200 °C.
  • the aminoalcohol compound represented by Chemical Formula 2 which is characterized by the present invention, does not have high basicity, but has a tertiary amine functional group and a hydroxy functional group simultaneously in one molecule.
  • the amine functionality and the hydroxy functionality at the reaction site effectively work to promote dehydration cyclization even at low temperatures below 200 ° C., thereby increasing the imidization rate of the polyamic acid.
  • the aminoalcohol compound represented by Chemical Formula 2 used as a catalyst in the process of dehydration of hydrogen atoms bonded to nitrogen atoms by water molecules falls through a state in which an amine functional group acts as a base to remove protons.
  • the hydroxy functional group can be assumed to act to stabilize the anionic oxygen atom of the cyclic intermediate through the proton of the hydroxy group.
  • the hydroxy functional group acts as a proton donor in the deprotonation stage to promote dehydration through proton transfer. That is, the amine functional group present in the aminoalcohol compound represented by Chemical Formula 2 proposed as a catalyst in the present invention acts as a base in the deprotonation reaction, and the hydroxy functional group is dehydrated by transferring protons to oxygen atoms of the cyclic intermediate.
  • these two functional groups are connected by a flexible carbon chain and control the imidization reaction by controlling the interval between the two working periods as the length of the carbon chain.
  • the aminoalcohol compound as the catalyst for the imidation reaction characterized in that the present invention is characterized in that, in Formula 2, R 1 , R 2 , R 3 , and R 4 each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a 1 to 12 carbon atom. Represents a hydroxyalkyl group, n is an aminoalcohol compound having an integer of 0 to 4;
  • R 1 and R 2 each represent an alkyl group having 1 to 12 carbon atoms
  • R 3 and R 4 each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxyalkyl group having 1 to 12 carbon atoms.
  • N is an aminoalcohol compound which is an integer of 0-4.
  • Particularly preferred catalysts for the imidization reaction are N, N -dimethylaminoethanol, N, N -diethylaminoethanol, N, N -dimethylaminopropanol, N, N -dimethylaminobutanol, N, N -dimethylaminobutane 2-ol, N, N -dimethylaminobutane-1,2-diol, N, N -diethylaminohexane-1,2-diol and the like can be used.
  • the aminoalcohol compound as the catalyst for the imidation reaction which is characterized by the present invention, has a low boiling point, and thus has an advantage of being easily removable even at a low temperature after the imidation reaction.
  • N, N -dimethylaminoethanol and N, N -diethylaminoethanol are liquid compounds having boiling points of 134 ° C. and 161 ° C., respectively, and this property completely removes the catalyst remaining in the film after polyimide resin formation. It shows a great advantage in removing.
  • 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] unde-7-cene and the like which have been conventionally used as imidization catalysts, have high boiling points of the compounds themselves. Therefore, there exists a problem that a residual amount increases in the inside of a film after polyimide resin formation.
  • the aminoalcohol compound as the catalyst for the imidation reaction which is characterized by the present invention, performs the catalysis smoothly even though the basicity and the nucleophilicity are not high, and also prevents the reverse reaction of the polyamic acid due to the low basicity and the nucleophilicity. Control effectively.
  • 1,4-diazabicyclo [2.2.2] octane and 1,8-diazabicyclo [5.4.0] unde-7-cene which are conventionally used as imidization catalysts, have high affinity due to their chemical structure.
  • the aminoalcohol compound as a catalyst for imidation reaction characterized by the present invention can be added to a polyamic acid solution and stored.
  • the catalyst of the present invention is a relatively mild aminoalcohol compound, which exhibits sufficient imidization efficiency with little degradation of the polyamic acid. This property is a process convenience that can be used in the polyimide film manufacturing process while pre-dissolving and storing the catalyst in the polyamic acid solution in the actual polyimide resin manufacturing process.
  • the amines conventionally used as imidization catalysts are difficult to be added and stored in the polyamic acid solution, there is a problem in the process of adding and dissolving them immediately when applying the polyamic acid solution to the support during the manufacturing process.
  • the aminoalcohol compound represented by the formula (2) as an imidization reaction catalyst characterized by the present invention is in the range of 1 to 200% by weight, preferably 1 to 100% by weight, more preferably 5 to 1, based on the polyamic acid solid content. It can be used in the range of 50% by weight.
  • the amount of the amino alcohol compound used as a catalyst is less than 1% by weight, the imidization reaction rate is remarkably low, and the effect as a catalyst is insignificant.
  • the amount is used in excess of 200% by weight, there is no enhanced catalytic effect. Since this is not the case, it is desirable to maintain the above range.
  • the aminoalcohol compound represented by Chemical Formula 2 according to the present invention has an excellent effect as an imidization catalyst, and this catalytic effect can be confirmed by comparing the results of Examples and Comparative Examples below. have.
  • a polyimide is prepared by performing an imidation reaction of a polyamic acid as is generally known in the art.
  • the production method may be performed by casting a polyamic acid solution on a general support, followed by imidization, to obtain a polyamide resin in the form of a film.
  • This casting method is only one embodiment, and the present invention is not limited to this casting method.
  • the support is generally used in the art and can be changed according to the desired form and parts, and the support selection is not particularly limited in the present invention.
  • the thickness of the polyimide film to be formed is not limited, but generally in the art, a film in the range of 100 nm to 500 ⁇ m is generally used. The reason for this is that if the thickness of the film is less than 100 nm, it is difficult to act as a thin film, and if it exceeds 500 ⁇ m, a problem arises in uniform film molding.
  • the imidation reaction carried out by the present invention can be carried out not only in the high temperature condition of 200 ° C. or higher, which is generally performed, but also in the low temperature range of less than 200 ° C.
  • the imidation reaction of the present invention can be specifically carried out within a wide temperature range of 100 ⁇ 400 °C. In other words, it is possible to produce a high-quality polyimide resin of interest even at a low temperature of 100 ⁇ 200 °C, which is not conventionally carried out, preferably carried out at 100 °C or more is good to minimize the amount of residual solvent and catalyst .
  • the imidization reaction temperature is less than 100 ° C., the removal of water dehydrated in the reaction is not smooth, resulting in deterioration of quality such as formation of fine pores in the film. If the temperature exceeds 400 ° C., oxidation and decomposition of the polyimide resin It is preferable to maintain the above temperature range because it may result in deterioration of the physical properties of the resin.
  • the polyamic acid used in the method for producing a polyimide according to the present invention is generally used for producing polyimide, and the present invention does not particularly limit the selection of the polyamic acid.
  • polyamic acid is prepared using aliphatic or aromatic tetracarboxylic dianhydride and aliphatic or aromatic diamine as raw materials, and in general, in order to obtain polyimide having high heat resistance and mechanical properties, aromatic acid dianhydride and aromatic diamine are preferable.
  • the tetracarboxylic dianhydride is generally used in the art, but is not particularly limited, but specifically 1,2,3,4-benzene tetracarboxylic dianhydride, which is a wholly aromatic acid dianhydride capable of giving a high packing structure, benzo Phenone tetracarboxylic dianhydride, bis (dicarboxyphenylether) dianhydride, bis (dicarboxyphenylmethane) dianhydride, bis (dicarboxyphenylsulfone) dianhydride, bis (dicarboxyphenylsulfide) dianhydride, bis (dicarboxy) Phenyl) propane dianhydride, bis (dicarboxyphenyl) hexafluoropropane dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride and fluorine-substituted derivatives
  • wholly aromatic diamine may be used, specifically p -phenylene diamine, m -phenylene diamine, diamino diphenyl ether, diamino diphenyl methane, diamino biphenyl, diamino dimethyl phenyl ether, diamino Dimethyl phenylmethane, diamino tetramethyl methyl phenyl methane, diamino diphenyl sulfone, diamino diphenyl sulfide, diamino benzophenone, bis (aminophenyl) propane, bis (aminophenyl) hexafluoropropane, diamino ditripulu Ormethyl biphenyl, diamino pyridine, diamino naphthalene, diamino dihydroxy biphenyl, bis (amino hydroxy phenyl) hexafluoropropane, 1,4-bisamin
  • diamine may be a diamine monomer containing a low polar alkyl group.
  • DA-IM-R 1 3-(3,5-diaminophenyl) -3-alkyl-succinimide
  • DA-OR 1 3,5-diaminophenyl-alkyl-ether
  • DA-Es-R 1 3,5-diaminophenyl-alkyl-amide
  • DA-AM-R 1 3,5-diaminophenyl-alkyl-amide
  • R 1 is a C1-C30 alkyl group or an aryl group, respectively.
  • the low polar group-containing diamine monomer can extend the surface tension control range of the polyimide insulator.
  • the low polar group-containing diamine monomer is used in the range of 0 to 100 mol% based on the total amount of diamine monomers, and at this time, the surface energy of the thin film can be controlled.
  • the reaction of the wholly aromatic acid dianhydride with the diamine is carried out in a solvent capable of dissolving these reactants and the polyamic acid of the desired product.
  • the solvent is not particularly limited in the art, but specifically, tetrahydrofuran, metaol, cyclohexanone, N, N -dimethylformamide, N, N -dimethylacetamide, N -methyl-2-pyrroli
  • One or more mixed solvents selected from don, cresol, pyridine, dimethylsulfoxide, ⁇ -butyrolactone, 2-butoxyethanol and 2-ethoxyethanol and the like.
  • the imidation ratio is 95 to 100%, and the amount of residual catalyst in the polyimide resin is 0. ⁇ 10 wt%.
  • the polyimide resin according to the present invention has a surface tension in the range of 30 to 65 dyne / cm, and a dielectric constant in the range of 2 to 6.
  • the polyimide resin produced by the above polymerization method has a weight average molecular weight (Mw) in the range of 10,000 to 500,000 g / mol, an intrinsic viscosity in the range of 1.0 to 3.0 g / dL, and a pyrolysis temperature in the range of 400 to 600 ° C.
  • Mw weight average molecular weight
  • the chemical resistance of the polyimide resin after curing was greatly improved.
  • the dielectric constant was in the range of 2-6 at the frequency of 10 KHz, and the surface tension was in the range of 30-65 dyne / cm.
  • the polyamic acid resin according to the present invention is a polymer material capable of imidization reaction at a low temperature process in the range of 100 to 200 ° C. by the introduction of a suitable organic catalyst as well as an improved electrical insulation property. This is useful as an insulator for all organic thin film transistors.
  • the organic thin film transistor fabricated from these is 0.01 ⁇ 3.0 cm 2 / Vs, preferably from 1 cm 2 / Vs or more, even more preferably from a high field-effect charge transfer of 1 ⁇ 3.0cm 2 / Vs range, -10 to 10 It has off-current characteristics in the range of 10 -13 A and hysteresis characteristics of less than 1 V.
  • an object of the present invention is to provide an organic thin film transistor device manufactured from a polyimide resin having excellent physical properties and capable of low temperature processing as an advanced industrial core material such as an organic thin film transistor.
  • Polyimide resin according to the invention has a weight average molecular weight (Mw) 10,000 To It is in the range of 500,000 g / mol, intrinsic viscosity 1.0-3.0 g / kV, pyrolysis temperature 450-550 ° C, dielectric constant 2-6 at a frequency of 10 KHz and surface tension 30-65 dyne / cm. It is also used as an insulating material for all organic thin film transistors. High field effect charge mobility, 10 -10 To 10 -13 It had off-current characteristics in the A range and hysteresis characteristics below 1 V.
  • Mw weight average molecular weight
  • the polyimide resin of the present invention has a low temperature process characteristics, excellent electrical properties, chemical resistance and heat resistance in the range of 100 ⁇ 200 °C as an insulating material for transistors insulators applied to all organic display devices, buffer coating layer of the color filter or Not only the application of the glass substrate and the liquid crystal display element for the touch panel (touch panel) as a polymer partition material is possible, but also the organic thin film transistor produced from these has the effect of providing excellent off current characteristics and excellent hysteresis characteristics.
  • Example 1 is a transistor characteristic (out put curve) of an organic thin film transistor device in which LPI-2 prepared in Example 2 is introduced as an insulator,
  • FIG. 2 is a hysteresis curve of the organic thin film transistor element in which LPI-2 prepared in Example 2 is introduced as an insulator.
  • NMP N -methyl-2-pyrrolidone
  • BPDA nonphthalic dianhydride
  • NMP N -methyl-2-pyrrolidone
  • the concentration of the solid content was 20% by weight, and the reaction was carried out for 3 hours while maintaining the reaction temperature at 0 ⁇ 10 °C.
  • the yield of the polymerization reaction was confirmed to be quantitative, and the intrinsic viscosity was measured at 30 ° C. at a concentration of 0.5 g / dl using N -methyl-2-pyrrolidone as a solvent.
  • 4 g of N, N -dimethylaminoethanol (10 wt% based on the polyamic acid solids) was added to the prepared polyamic acid solution, stirred for 10 minutes, spin-coated, and imidized at 60 ° C. for 60 minutes.
  • LPI-4 polyimide thin film
  • the thickness of the polyimide thin film was controlled in the range of 1,000 mm 3, and the degree of imidization was measured using an FT-IR spectrometer.
  • the concentration of the solid content was 20% by weight, and the reaction was carried out for 3 hours while maintaining the reaction temperature at 0 ⁇ 10 °C.
  • the yield of the polymerization reaction was confirmed to be quantitative, and the intrinsic viscosity was measured at 30 ° C. at a concentration of 0.5 g / dl using N -methyl-2-pyrrolidone as a solvent.
  • 4 g of N, N -dimethylaminoethanol (10 wt% based on the polyamic acid solids) was added to the prepared polyamic acid solution, stirred for 10 minutes, spin-coated, and imidized at 60 ° C. for 60 minutes.
  • LPI-6 polyimide thin film
  • the thickness of the polyimide thin film was controlled in the range of 1,000 mm 3, and the degree of imidization was measured using an FT-IR spectrometer.
  • a polyimide resin (LPI-7) was prepared in the same manner as in Example 1, using 5 wt% of N, N -dimethylaminoethanol based on the polyamic acid solid content.
  • Example 2 In the same manner as in Example 1, 25 wt% of N, N -dimethylaminoethanol was introduced based on the polyamic acid solid content, and the polyimide resin (LPI-9 was subjected to an imidization reaction at a temperature of 130 ° C. for 60 minutes. ) was prepared.
  • N N -dimethylaminoethanol was introduced in an amount of 30% by weight based on the polyamic acid solid content, and the polyimide resin (LPI-10) was subjected to an imidization reaction at a temperature of 100 ° C. for 60 minutes. ) was prepared.
  • the monomer composition and intrinsic viscosity of the polyamic acid prepared according to Examples 1 to 10 and Comparative Examples 1 to 3 are shown in Table 1 below.
  • the intrinsic viscosity of the soluble polyimide resin of the present invention was 1.28 ⁇ 2.64 dl / g, the weight average molecular weight measured by gel permeation chromatography (GPC) was in the range of 10,000 ⁇ 500,000 g / mol and the film formability by solvent casting This appeared to be very excellent.
  • the solvent was removed by heat treatment at a temperature of 90 ° C. for 2 minutes. Then, the polyimide thin film was prepared by drying for 60 to 120 minutes at a temperature between 100 ⁇ 400 °C.
  • a polyimide thin film was prepared by varying the thermal curing conditions of the polyamic acid solution and the type of catalyst, and after heat treatment for 60 to 120 minutes at a temperature range of 100 to 400 ° C., stability to the porter resist stripper and the etchant.
  • the evaluation results are shown in Table 2 below.
  • the polyimide resins prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were thermally treated at 100 to 400 ° C. after the thin film coating, and then thermogravimetric analysis was performed. Was used to determine the initial decomposition temperature. In addition, HPLC was used to measure the amount of catalyst residue remaining in the thin film, and the results are shown in Table 2 below.
  • the residual catalyst amount in the thin film of the present invention showed a low experimental result of 200 ppm or less, whereas the 1,8-diazabicyclo [5.4.0] of Comparative Example 1 When unde-7-cene was used as a catalyst, the value was higher than 2000 ppm.
  • the polyimide thin films of Examples 1 to 10 exhibited a high pyrolysis temperature in the range of 480 to 550 ° C. The results are shown in Table 3 below.
  • the organic thin film transistor was manufactured using the low temperature hardening type polyimide of this invention, and the characteristic was measured.
  • As an organic semiconductor pentacene, which is widely used in organic thin film transistors and has a relatively good performance, was used.
  • Substrates used glass or plastic substrates such as polyethersulfone. The method of manufacturing a top-contact device is as follows.
  • Pentacene an organic semiconductor
  • Pentacene an organic semiconductor
  • the temperature of the substrate having a great influence on the crystallization of pentacene was kept constant at 90 ⁇ 140 °C.
  • gold was deposited to a thickness of 40 nm in the same manner as gate deposition to form a source and a drain electrode.
  • Bottom-contact devices were fabricated by changing the order of formation of pentacene, source, and drain electrodes.
  • the characteristics of the device manufactured as described above were measured in the saturation region by measuring the drain voltage-drain current according to the gate voltage and the gate voltage-drain current curve according to the drain voltage using an E5272 device manufactured by Agilent Technologies. Various characteristics were evaluated using the current and voltage equations.
  • the polyimide resins prepared according to Examples 1 to 10 of the present invention had a dielectric constant in the range of 2.0 to 6.0 and surface energy in the range of 30 to 65 dyne / cm and octadecyl in the polymer.
  • LPI-6 with DA-L-18IM a monomer containing side chain groups, exhibited the lowest dielectric constant and surface energy.
  • the increase in the degree of imidization and the decrease in the surface energy showed the effect of increasing the field effect charge mobility, and as a result, the excellent field effect charge mobility.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention porte sur un film isolant de polyimide, obtenu à partir d'une composition de résine polyamique durcissable à basse température et sur un transistor en couches minces tout organique l'utilisant. Plus spécifiquement, la présente invention porte sur un dispositif transistor en couches minces tout organique, dans lequel un dianhydride tétracarboxylique aromatique ayant une structure de tassement élevée et un monomère diamine aromatique sont polymérisés pour préparer une résine d'acide polyamique, et la résine résultante est ensuite soumise à une imidation en présence d'un catalyseur organique durcissable à basse température ayant un faible point d'ébullition qui est contenu comme composition essentielle, de telle sorte qu'une imidation à basse température est possible à une plage de température de 100 à 200°C et le résidu de catalyseur après un traitement en couches minces est très faible, tel que de 200 ppm ou moins, conférant d'excellentes propriétés de transistor au dispositif de transistor en couches minces tout organique.
PCT/KR2009/005694 2009-07-08 2009-10-06 Matériau isolant de polyimide durcissable à basse température obtenu à partir d'une composition de résine d'acide polyamique ayant une structure de tassement élevée, et dispositif transistor à couches minces tout organique ayant de faibles propriétés d'hystérésis conférées par la composition Ceased WO2011004938A1 (fr)

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CN104558607A (zh) * 2010-07-14 2015-04-29 株式会社Lg化学 可低温固化的聚酰亚胺树脂及其制备方法
CN107108887A (zh) * 2014-12-30 2017-08-29 韩国爱思开希可隆Pi股份有限公司 交联型水溶性热塑性聚酰胺酸及其制备方法
CN110431696A (zh) * 2017-03-15 2019-11-08 日本电气株式会社 二次电池用粘合剂组合物
WO2020232338A1 (fr) * 2019-05-15 2020-11-19 Promerus, Llc Compositions photosensibles à ton positif contenant de l'acide amique en tant que catalyseur de base latent
CN112088201A (zh) * 2018-11-08 2020-12-15 株式会社Lg化学 液晶取向剂组合物、制备液晶取向膜的方法、以及使用其的液晶取向膜、液晶显示器
CN112574443A (zh) * 2019-09-30 2021-03-30 Sk新技术株式会社 聚酰亚胺类薄膜及包括其的柔性显示面板
CN114736408A (zh) * 2022-03-23 2022-07-12 哈尔滨理工大学 一种高介电pi/pvdf复合薄膜的制备方法
CN114920934A (zh) * 2022-06-29 2022-08-19 深圳职业技术学院 一种感光聚酰亚胺树脂的制备方法和应用

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KR101485866B1 (ko) * 2013-04-23 2015-01-27 한국화학연구원 신규한 폴리이미드 중합체, 이의 제조방법 및 이를 이용한 유기절연막
WO2015183056A1 (fr) * 2014-05-30 2015-12-03 주식회사 엘지화학 Liquide à base de polyimide et film à base de polyimide produit en l'utilisant
KR101720626B1 (ko) * 2015-06-04 2017-04-03 한국화학연구원 폴리이미드 및 폴리비닐알콜을 포함하는 이중층 유기 절연체 및 이를 이용한 박막 트랜지스터
KR101973192B1 (ko) 2017-06-29 2019-04-26 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 및 이를 이용한 액정 배향막
KR102461121B1 (ko) * 2019-02-21 2022-10-28 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 이를 이용한 액정 배향막 및 액정표시소자

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KR19990028291A (ko) * 1995-06-23 1999-04-15 캔디 매드록 강염기 3차 아미노 알코올 촉매
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CN104558607A (zh) * 2010-07-14 2015-04-29 株式会社Lg化学 可低温固化的聚酰亚胺树脂及其制备方法
CN107108887A (zh) * 2014-12-30 2017-08-29 韩国爱思开希可隆Pi股份有限公司 交联型水溶性热塑性聚酰胺酸及其制备方法
CN107108887B (zh) * 2014-12-30 2020-07-03 韩国爱思开希可隆Pi股份有限公司 交联型水溶性热塑性聚酰胺酸及其制备方法
CN110431696B (zh) * 2017-03-15 2022-12-06 日本电气株式会社 二次电池用粘合剂组合物
CN110431696A (zh) * 2017-03-15 2019-11-08 日本电气株式会社 二次电池用粘合剂组合物
CN112088201A (zh) * 2018-11-08 2020-12-15 株式会社Lg化学 液晶取向剂组合物、制备液晶取向膜的方法、以及使用其的液晶取向膜、液晶显示器
CN112088201B (zh) * 2018-11-08 2023-09-05 株式会社Lg化学 液晶取向剂组合物、制备液晶取向膜的方法、以及使用其的液晶取向膜、液晶显示器
WO2020232338A1 (fr) * 2019-05-15 2020-11-19 Promerus, Llc Compositions photosensibles à ton positif contenant de l'acide amique en tant que catalyseur de base latent
US11061328B2 (en) 2019-05-15 2021-07-13 Promerus, Llc Positive tone photosensitive compositions containing amic acid as latent base catalyst
TWI811543B (zh) * 2019-05-15 2023-08-11 日商住友電木股份有限公司 含有醯胺酸作為潛含性鹼觸媒之正色調感光性組成物
CN112574443A (zh) * 2019-09-30 2021-03-30 Sk新技术株式会社 聚酰亚胺类薄膜及包括其的柔性显示面板
CN114736408A (zh) * 2022-03-23 2022-07-12 哈尔滨理工大学 一种高介电pi/pvdf复合薄膜的制备方法
CN114736408B (zh) * 2022-03-23 2024-01-26 哈尔滨理工大学 一种高介电pi/pvdf复合薄膜的制备方法
CN114920934A (zh) * 2022-06-29 2022-08-19 深圳职业技术学院 一种感光聚酰亚胺树脂的制备方法和应用
CN114920934B (zh) * 2022-06-29 2024-03-22 深圳职业技术学院 一种感光聚酰亚胺树脂的制备方法和应用

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