WO2015111982A1 - Polyimide et film utilisant ce polyimide - Google Patents

Polyimide et film utilisant ce polyimide Download PDF

Info

Publication number
WO2015111982A1
WO2015111982A1 PCT/KR2015/000812 KR2015000812W WO2015111982A1 WO 2015111982 A1 WO2015111982 A1 WO 2015111982A1 KR 2015000812 W KR2015000812 W KR 2015000812W WO 2015111982 A1 WO2015111982 A1 WO 2015111982A1
Authority
WO
WIPO (PCT)
Prior art keywords
dianhydride
bis
polyimide
acid
diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2015/000812
Other languages
English (en)
Korean (ko)
Inventor
박효준
정학기
하창식
쿠마르 타파쉬프라딥
정영식
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kolon Industries Inc
Original Assignee
Kolon Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020140058606A external-priority patent/KR101574016B1/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Priority to ES15740323T priority Critical patent/ES2835954T3/es
Priority to EP15740323.9A priority patent/EP3101049B1/fr
Priority to CN201580006169.0A priority patent/CN105940039B/zh
Priority to JP2016548697A priority patent/JP6625993B2/ja
Priority to US15/114,093 priority patent/US9657140B2/en
Publication of WO2015111982A1 publication Critical patent/WO2015111982A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide and a film using the same, and more particularly, to a polyimide having excellent thermal stability and low dielectric constant and excellent light transmittance while maintaining excellent physical properties of the polyimide, and a polyimide film comprising the same. It is about.
  • polyimides have high mechanical strength, heat resistance, insulation, solvent resistance, and the like, and thus are widely used as electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display devices and semiconductors.
  • optical communication materials such as optical waveguide materials and use as substrates for mobile phones are also expected.
  • polyimide that is not only excellent in heat resistance and solvent resistance but also has a large number of performances depending on the application such as transparency is desired.
  • the wholly aromatic polyimide obtained by the polycondensation reaction of the aromatic tetracarboxylic dianhydride and aromatic diamine which is conventionally used generally has a dark amber color, there exists a problem in the use which requires high transparency.
  • the wholly aromatic polyimide has a high dielectric constant, there is a limit to being used as an electronic material requiring transparency and low dielectric constant.
  • a polyimide precursor is obtained by polycondensation reaction of an alicyclic tetracarboxylic dianhydride and an aromatic diamine, and imidation of the precursor results in relatively little coloring and a high transparency polyimide. What is obtained is known (Japanese Patent Laid-Open No. 2-24294, Japanese Patent Laid-Open No. 58-208322).
  • organic electroluminescence (hereinafter abbreviated as organic EL). Flagship) Use as a gas barrier film of an element is examined (Japanese Patent Laid-Open No. 2006-232960).
  • the polyimide produced by such a method has not only room for improvement in terms of low degree of polymerization and heat resistance, but also not necessarily sufficient optical properties.
  • the main object of the present invention is to provide a polyimide and a polyimide film comprising the same, which exhibits excellent thermal stability and low dielectric constant while maintaining excellent physical properties of the polyimide, while having excellent light transmittance.
  • one embodiment of the present invention is a polyimide obtained by imidizing a polyamic acid polymerized diamine and acid dianhydride, the acid dianhydride includes a compound represented by the following formula (1) It provides a polyimide characterized in that.
  • the diamine is p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 1,3-bis (4,4 ' -Aminophenoxy) benzene, 4,4'-diamino-1,5-phenoxypentane, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane , Bis (3,5-diethyl-4-aminophenyl) methane, diaminodiphenylsulfone, diaminobenzophenone, diaminon
  • the diamine is 1,6-hexamethylenediamine (16DAH), 1,12-diaminododecane (112DAD), 4,4'-diaminodicyclohexylmethane (MCA) and It may be characterized by at least one member selected from the group consisting of 4,4'-methylene bis (2-methyl cyclohexylamine) (MMCA).
  • the acid dianhydride is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4- (2,5-dioxotetrahydro Furan-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), pyromellitic dianhydride (1,2,4,5-benzene Tetracarboxylic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), biscarboxyphenyl Dimethyl silane dianhydride (SiDA), bis dicarboxyphenoxy diphenyl sulfide dianhydride (BDSDA), sulfonyl diphthalic hydride (SO 2 DPA), cycl
  • Another embodiment of the present invention provides a polyimide film comprising the polyimide.
  • the polyimide film may have a transmittance of 80% or more at 550 nm based on a film thickness of 10 to 100 ⁇ m, and a dielectric constant of 1 GHz to 3.3 or less.
  • the present invention exhibits low dielectric constant while maintaining excellent physical properties of polyimide, and includes polyimides useful as optical communication materials such as optical waveguides, electronic materials such as protective materials and insulating materials in liquid crystal display devices and semiconductors, and the like.
  • a polyimide film can be provided.
  • the present invention provides a polyimide obtained by imidizing a polyamic acid polymerized with diamine and an acid dianhydride, wherein the acid dianhydride includes a compound represented by the following Chemical Formula 1, and the polyimide comprises the polyimide. It relates to a polyimide film.
  • aliphatic polyimides have low molecular weight, bipolarity, and intermolecular or intramolecular charge transfer properties in comparison to aromatic polyimides, so they have high solubility in organic solvents, high transparency, and low dielectric constant. It is attracting much attention as an optoelectronic and interlayer insulating material.
  • piperazine-disuccinic anhydride (acid dianhydride represented by Chemical Formula 1) containing nitrogen is used as an acid dianhydride to prepare aliphatic polyimide having high transparency and low dielectric constant. Used.
  • Acid dianhydride represented by the formula (1) according to the present invention contains one or more nitrogen atoms in the molecule, thereby causing the interaction of the intramolecular or intermolecular chain due to the isolated electron pair of the nitrogen atom, thereby using the intrinsic polyimide It can greatly improve the solubility and electrical properties of the polyimide while maintaining the excellent properties of.
  • Acid dianhydride according to the present invention can be prepared by a very simple organic synthesis method such as Michael addition reaction and hydrolysis reaction.
  • the method for preparing an acid dianhydride according to the present invention reacts the compound represented by the formula (2) with piperazine to produce the compound represented by the formula (3), and hydrolyzes the compound represented by the formula (3) in the presence of a base catalyst To produce a compound represented by Formula 4, and then a dehydrating agent was added to prepare an acid dianhydride represented by Formula 1 below.
  • the compound represented by the formula (3) is produced by the Michael addition reaction of the compound represented by the formula (2) (dimethyl fumalate) and piperazine.
  • the compound represented by the formula (2) in the Michael addition reaction (dimethyl fumarate) is Michael acceptor (acceptor)
  • piperazine is Michael donor (donor).
  • the Michael addition reaction is preferably performed for 4 to 16 hours at 20 ⁇ 140 °C in terms of reaction efficiency.
  • the compound represented by Chemical Formula 2 and piperazine may be preferably used in a yield ratio of 1: 0.45 to 1: 0.55.
  • the compound represented by Chemical Formula 2 may be prepared by various known methods.
  • fumaric acid is added to methanol, refluxed by adding an acid catalyst such as sulfuric acid, and neutralized with a neutralizing agent such as sodium carbonate. It can manufacture.
  • reaction material itself as a solvent as the reaction mode
  • other reaction solvents may be used.
  • the reaction solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof may include 1,4-dioxane, toluene, N-Methyl-2-pyrrolidone (NMP), and dimethylacetamide (DMAc).
  • the compound represented by Formula 3 thus produced generates a compound represented by Formula 4 by hydrolysis in the presence of a base catalyst.
  • the hydrolysis reaction may be performed at 40 to 120 ° C. for 1 to 6 hours, sufficient reaction may occur to reduce unreacted materials, prevent evaporation of the solvent and catalyst, and may be preferable in terms of cost and efficiency. have.
  • the base catalyst used in the hydrolysis reaction may be at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide and magnesium hydroxide, preferably potassium hydroxide in terms of price and ease of handling, Sodium hydroxide and the like.
  • the base catalyst may be used in an amount of 5 to 10 moles with respect to 1 mole of the compound represented by Chemical Formula 3, and the amount of hydrochloric acid precipitated by using an appropriate amount of base catalyst in the progress of the hydrolysis reaction may be appropriately adjusted within this range. It may be advantageous in terms of efficiency and productivity.
  • compound represented by the formula (4) is a dehydrating agent (dehydrating agent) is added to the compound represented by the formula (4), the aliphatic acid dianhydride represented by the formula (1) by the dehydration ring closure reaction.
  • the dehydration ring-closure reaction is performed for 4 to 28 hours at 40 ⁇ 100 °C, to prevent the evaporation of the catalyst and the solvent to improve the yield and the reaction time is appropriate while inducing a sufficient reaction time to improve the yield May be preferred.
  • the dehydrating agent may be at least one selected from the group consisting of tertiary amines such as acetic anhydride, pyridine, isoquinoline, triethylamine and the like, and in terms of efficiency, it is preferable to use acetic anhydride and / or pyridine.
  • the content of the dehydrating agent may be 2 or more moles, preferably 2 to 10 moles with respect to 1 mole of the compound represented by the formula (4). This range of use may lead to sufficient reaction to improve the yield and may be advantageous in terms of cost.
  • the resultant compound is filtered by a conventional method and then dried to prepare an acid dianhydride represented by the formula (1).
  • the acid dianhydride represented by the general formula (1) of the present invention described above may be prepared into a polyimide by preparing a polyamic acid by diamine and a polycondensation reaction, followed by dehydration ring closure using heat or a catalyst. At this time, the equivalent ratio of the diamine: acid dianhydride is preferably 1: 1.
  • the said diamine is not specifically limited, Various diamines conventionally used for polyimide synthesis can be used. Specific examples thereof include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 1,3-bis (4,4'-aminophenoxy) benzene, 4 , 4'-diamino-1,5-phenoxypentane, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy- 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylpropane, bis (3,5-di Ethyl-4-aminophenyl) methane, diaminodiphen
  • the diamine of the present invention may be 1,6-hexamethylenediamine (also referred to as 1,6-diaminohexane, 16DAH), 1,12-diaminododecane (1,12-diaminododecane, 112DAD), 4,4'-diaminodicyclohexylmethane (also referred to as 4,4'-methylene bis (cyclohexylamine), MCA) and 4,4'-methylene bis (2-methyl cyclohexylamine) (4, It may be one or more selected from the group consisting of 4'-methylene bis (2-methyl cyclohexylamine, MMCA).
  • the present invention also provides a 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) within a range that does not inhibit polyimide physical properties other than the acid dianhydride represented by the formula (1).
  • 6FDA 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
  • TDA pyromellitic dian Hydrides (1,2,4,5-benzene tetracarboxylic dianhydride, PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), oxy Diphthalic dianhydride (ODPA), biscarboxyphenyl dimethyl silane dianhydride (SiDA), bis dicarboxyphenoxy diphenyl sulfide dianhydride (BDSDA), sulfonyl diphthalic hydride (SO 2 DPA), cyclo Butane tetracarboxylic dianhydride (CBDA), isof Filidenephenoxy bis phthalic anhydride (6HBDA), bicyclo [2.2.2
  • the present invention in terms of improving optical properties and dielectric constant, preferably 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) containing fluorine which can increase free volume.
  • 6FDA 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
  • the content of the acid dianhydride additionally included may be expected to improve the heat resistance in a range of 80 mol% or less, preferably 10 to 50 mol% relative to the total moles of acid dianhydride does not inhibit the optical properties and dielectric constant. .
  • the method for obtaining the polyamic acid of the present invention is not particularly limited, and the acid dianhydride represented by the general formula (1) and the diamine may be reacted and polymerized by a known production method, but the acid dianhydride represented by the general formula (1) in an organic solvent.
  • the method of mixing and reacting with diamine is simple.
  • organic solvent used examples include m-cresol, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and N.
  • NMP N-methyl-2-pyrrolidone
  • DMF N-dimethylformamide
  • DMAc N-dimethylacetamide
  • N. -Methyl caprolactam dimethyl sulfoxide (DMSO), tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, gamma -butyrolactone, etc.
  • These solvents may be used alone or in combination of two or more thereof.
  • it is a solvent which does not melt a polyamic acid, you may add to and use the said solvent within the range from which a uniform solution is obtained.
  • the reaction temperature of solution polymerization can select arbitrary temperature of -20-150 degreeC, Preferably -5-100 degreeC.
  • the molecular weight of a polyamic acid can be controlled by changing the molar ratio of the acid dianhydride represented by General formula (1) used for reaction, and diamine, and similar to a normal polycondensation reaction, the polya produced as this molar ratio approaches 1, The molecular weight of the acid is increased.
  • the method of dehydrating and ringing a polyamic acid in order to obtain a polyimide from a polyamic acid is not specifically limited, but similarly to the conventional polyamic acid, the method of ring closure by heating or chemically ringing using a well-known dehydration ring closure catalyst is employ
  • the heating method can be stepped up step by step from 80 °C to 300 °C.
  • the method of chemically ring closing can be performed in presence of organic bases, such as a pyridine and a triethylamine, and acetic anhydride, etc., and the temperature at this time can select arbitrary temperature of -20-200 degreeC.
  • organic bases such as a pyridine and a triethylamine, and acetic anhydride, etc.
  • the polymerization solution of polyamic acid can be used as it is or diluted.
  • an organic solvent at this time the polymerization solvent of the polyamic acid mentioned above is mentioned.
  • the polyimide (containing) solution thus obtained may be used as it is, or a solvent such as methanol or ethanol may be added to precipitate the polymer, which is isolated and re-dissolved as a powder or in a suitable solvent for use. Can be.
  • the solvent for re-dissolution is not particularly limited as long as it dissolves the obtained polymer.
  • m-cresol, 2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, and N-vinyl-2-pyrroli DON, DMAc, DMF (dimethylformamide), (gamma) -butyrolactone, etc. are mentioned.
  • the polyimide film of the present invention can be obtained by casting polyamic acid on a support and dehydrating and closing the ring in the same manner as described above.
  • the rate of change (dehydration closure rate) from polyamic acid to polyimide is defined as the imidization rate, but the imidation rate of the polyimide of the present invention is not limited to 100%, and optionally 1 to 100%. You can select the value of.
  • the thermal hysteresis and residual stress remaining in the film can be solved to obtain stable thermal stability and to have an excellent coefficient of thermal expansion.
  • the residual volatile content of the film after heat treatment is 5% or less, and preferably 3% or less.
  • the thickness of the polyimide film manufactured in this way is not specifically limited, It is preferable that it is the range of 10-250 micrometers, More preferably, it is 10-100 micrometers.
  • a polyimide and a polyimide film can be prepared by imidating a polyamic acid obtained by reacting with a diamine and an acid dianhydride, and the polyimide film thus prepared is N-methyl-2- High solubility in organic solvents such as pyrrolidone (N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl phthalate (DMP) and dimethylsulfoxide (DMSO)
  • NMP N-methyl-2-pyrrolidone
  • DMAc dimethylacetamide
  • DMP dimethyl phthalate
  • DMSO dimethylsulfoxide
  • the polyimide film according to the present invention exhibits a low dielectric constant and is colorless and transparent, which is useful for use as an optical communication material such as an optical material such as an electronic material such as a protective material or an insulating material in a liquid crystal display device or a semiconductor. .
  • the obtained compound represented by the formula (3) measured the melting point (Buchi, M-560), and also NMR ( 1 H and 13 C) (JEOL, JNM-LA400) and IR (AVATAR, 360 FT-IR) Analyzed using.
  • the washed precipitate was dried in a vacuum oven for 24 hours, and recrystallized in 2,000 ml of a mixture of water and methanol in a 1: 1 ratio to obtain 8.7 g of a compound represented by Formula 4 (yield 92%).
  • the obtained compound represented by the formula (4) is not soluble in a general organic solvent and water mixed with the compound represented by the formula (4) in heavy water (D 2 O) in which solid potassium hydroxide is dissolved in order to make an NMR sample for NMR analysis Used.
  • the melting point (Buchi, M-560) was measured, NMR ( 1 H and 13 C) (JEOL, JNM-LA400) and IR (AVATAR, 360 FT-IR) It was analyzed using.
  • the obtained polyimide films were able to identify characteristic 1771-1775 cm -1 absorption bands appearing in the imide through FTIR (AVATAR 360 FT-IR) (FIG. 1). This is due to the asymmetric stretching of the carbonyl group, and 1691-1697 cm -1 is due to the symmetric stretching of the carbonyl group. Due to the absence of the aromatic ring, the nonconjugated structure of the imide carbonyl group is the It can be confirmed that it causes the change of absorption.
  • Example 1 Example 2
  • Example 3 Diamine Type 1,6-hexamethylene diamine (16DAH) 1,12-diaminododecane (112DAD) 4,4'-diaminodicyclohexylmethane (MCA) 4,4'-methylene bis (2-methylcyclohexylamine) (MMCA)
  • a portion of the polycondensation solution containing polyamic acid was cast on a glass plate, and the glass plate was heated under vacuum for 3 hours at 80 ° C., 1 hour at 200 ° C. and 1 hour at 250 ° C. to obtain a polyimide film. After curing, the film was removed from the glass plate by immersing the glass plate in hot water to remove the flexible and support-free polyimide film to prepare a polyimide film having a thickness of 15 ⁇ m.
  • a polyimide film was prepared in the same manner as in Example 1, but a polyimide film (thickness 15 ⁇ m) was prepared using pyromellitic dianhydride (PMDA) as an acid dianhydride.
  • PMDA pyromellitic dianhydride
  • a polyimide film was prepared in the same manner as in Example 1, except that pyromellitic dianhydride (PMDA) and diamine were used as an acid dianhydride (4,4'-oxydianiline, ODA). ) And N, N-dimethyl acetamide as a solvent to prepare a polyimide film (thickness 15 ⁇ m).
  • PMDA pyromellitic dianhydride
  • ODA acid dianhydride
  • N, N-dimethyl acetamide as a solvent to prepare a polyimide film (thickness 15 ⁇ m).
  • Polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (Waters: Waters707).
  • the polymer to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 ⁇ l was injected into GPC.
  • the mobile phase of GPC used tetrahydrofuran and was introduced at a flow rate of 1.0 mL / min, and the analysis was performed at 35 ° C.
  • the column connected four Waters HR-05,1,2,4E in series.
  • the detector was measured at 35 ° C using RI and PAD Detecter.
  • molecular weight distribution (PDI) was calculated by dividing the measured weight average molecular weight (Mw) by the number average molecular weight (Mn).
  • the transmittance at 550 nm was measured using a UV spectrometer (Konita Minolta, CM-3700d).
  • K is the dielectric constant
  • C is the capacitance
  • d is the film thickness
  • A is the specimen (film) area (2 ⁇ 2 mm)
  • ⁇ o is the dielectric constant of vacuum (8.85 ⁇ 10 ⁇ 12) Fm -1 ).
  • the second value was calculated as glass transition temperature (Tg) by performing a 2nd run from 50 ° C to 300 ° C at a heating rate of 10 ° C / min using a Perkin Elmer DSC7 device.

Landscapes

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

Abstract

L'invention concerne un polyimide et un film utilisant ce polyimide. L'invention concerne plus précisément un polyimide présentant une constante diélectrique faible tout en conservant les propriétés physiques remarquables du polyimide non modifié, ledit polyimide étant utilisé comme matériau pour communication optique, par exemple un guide d'onde optique, ou comme matériau électronique, par exemple un matériau protecteur ou un matériau isolant dans un élément d'affichage à cristaux liquides ou un semi-conducteur.
PCT/KR2015/000812 2014-01-27 2015-01-26 Polyimide et film utilisant ce polyimide Ceased WO2015111982A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES15740323T ES2835954T3 (es) 2014-01-27 2015-01-26 Poliimida y película que la utiliza
EP15740323.9A EP3101049B1 (fr) 2014-01-27 2015-01-26 Polyimide et film utilisant ce polyimide
CN201580006169.0A CN105940039B (zh) 2014-01-27 2015-01-26 聚酰亚胺以及使用该聚酰亚胺的薄膜
JP2016548697A JP6625993B2 (ja) 2014-01-27 2015-01-26 ポリイミド及びこれを用いたフィルム
US15/114,093 US9657140B2 (en) 2014-01-27 2015-01-26 Polyimide and film using same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20140009483 2014-01-27
KR10-2014-0009483 2014-01-27
KR1020140058606A KR101574016B1 (ko) 2014-01-27 2014-05-15 폴리이미드 및 이를 이용한 필름
KR10-2014-0058606 2014-05-15

Publications (1)

Publication Number Publication Date
WO2015111982A1 true WO2015111982A1 (fr) 2015-07-30

Family

ID=53681700

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/000812 Ceased WO2015111982A1 (fr) 2014-01-27 2015-01-26 Polyimide et film utilisant ce polyimide

Country Status (1)

Country Link
WO (1) WO2015111982A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023065489A1 (fr) * 2021-10-21 2023-04-27 中国科学院深圳先进技术研究院 Composé hautement diélectrique et procédé de préparation associé, matériau époxy hautement diélectrique et procédé de préparation associé, et dispositif à semi-conducteur

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58208322A (ja) 1982-05-31 1983-12-05 Japan Synthetic Rubber Co Ltd ポリイミド化合物の製造方法
JPH0224294B2 (fr) 1984-03-09 1990-05-29 Nissan Chemical Ind Ltd
JP2006232960A (ja) 2005-02-24 2006-09-07 Fuji Photo Film Co Ltd 光学フィルムおよび画像表示装置
JP2009013165A (ja) * 2007-06-06 2009-01-22 Chisso Corp 酸二無水物、液晶配向膜および液晶表示素子
JP2009175684A (ja) * 2007-12-26 2009-08-06 Chisso Corp 液晶配向剤、液晶配向膜及び液晶表示素子
JP2011203703A (ja) * 2010-03-04 2011-10-13 Jnc Corp 液晶表示素子、その液晶表示素子を作製する工程で用いられる液晶配向剤、およびその液晶配向剤を用いて形成される液晶配向膜

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58208322A (ja) 1982-05-31 1983-12-05 Japan Synthetic Rubber Co Ltd ポリイミド化合物の製造方法
JPH0224294B2 (fr) 1984-03-09 1990-05-29 Nissan Chemical Ind Ltd
JP2006232960A (ja) 2005-02-24 2006-09-07 Fuji Photo Film Co Ltd 光学フィルムおよび画像表示装置
JP2009013165A (ja) * 2007-06-06 2009-01-22 Chisso Corp 酸二無水物、液晶配向膜および液晶表示素子
JP2009175684A (ja) * 2007-12-26 2009-08-06 Chisso Corp 液晶配向剤、液晶配向膜及び液晶表示素子
JP2011203703A (ja) * 2010-03-04 2011-10-13 Jnc Corp 液晶表示素子、その液晶表示素子を作製する工程で用いられる液晶配向剤、およびその液晶配向剤を用いて形成される液晶配向膜

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
C. B. POLLARD ET AL.: "DERIVATIVES OF PIPERAZINE. III. REACTIONS WITH UNSATURATED ESTERS, PART 1", J. AM. CHEM. SOC., vol. 57, no. 1, 1 January 1935 (1935-01-01), pages 199 - 200, XP055357365 *
CARR G.; WILLIAMS D. E.; DI'AZ-MARRERO A. R.; PATRICK B. 0.; BOTTRIELL H.; BALGI A. D.; DONOHUE E.; ROBERGE M.; ANDERSEN R. J., J. NAT. PROD., vol. 73, 2010, pages 422
RON HULST ET AL.: "ASYMMETRIC SYNTHESIS OF NEW CHIRAL EUROPIUM N,N'-DISUCCINATE COMPLEXES: SHIFT REAGENTS FOR AQUEOUS SOLUTIONS AND APPLICATION IN THE ENANTIOMERIC EXCESS DETERMINATION OF AMINO ACIDS", J. ORG. CHEM., vol. 59, no. 24, 1994, pages 7453 - 7458, XP002287633 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023065489A1 (fr) * 2021-10-21 2023-04-27 中国科学院深圳先进技术研究院 Composé hautement diélectrique et procédé de préparation associé, matériau époxy hautement diélectrique et procédé de préparation associé, et dispositif à semi-conducteur

Similar Documents

Publication Publication Date Title
JP6796163B2 (ja) ポリイミドの製造方法
WO2015174567A1 (fr) Polyimide et film l'utilisant
WO2013133508A1 (fr) Composé diamine ayant deux substituants dans une structure asymétrique, et polymère préparé en utilisant celui-ci
JP6087446B2 (ja) 低い熱膨張係数を有する新規なポリアミドイミド
WO2017003173A1 (fr) Solution de précurseur de polyimide-polybenzoxazole, film de polyimide-polybenzoxazole et procédé de préparation correspondant
US5470943A (en) Polyimide
KR20190005851A (ko) 폴리이미드 수지
KR102564254B1 (ko) 고리형 탄화수소 골격 및 에스테르기를 가지는 테트라카르본산 이무수물, 폴리아믹산 및 폴리이미드
WO2019132515A1 (fr) Procédé de préparation d'acide polyamique, et acide polyamique, résine de polyimide et film de polyimide ainsi fabriqués
WO2018062887A1 (fr) Acide polyamique, polyimide, film de polyimide, dispositif d'affichage d'image comprenant le film et procédé de préparation d'acide polyamique
JP6145571B2 (ja) 新規酸二無水物、及びこの製造方法
KR20140106566A (ko) 비스(하이드록시아미드)형 산 2 무수물, 그 제조법 및 폴리이미드
KR20070116228A (ko) 폴리아믹산, 폴리이미드 및 그 제조 방법
WO2015111982A1 (fr) Polyimide et film utilisant ce polyimide
KR102335654B1 (ko) 테트라카르복실산 2 무수물, 폴리아믹산 및 폴리이미드
WO2016190170A1 (fr) Dianhydride d'acide tétracarboxylique présentant un squelette d'hydrocarbure cyclique et un groupe ester, acide polyamique et polyimide
WO2016129926A1 (fr) Acide polyamique, résine de polyimide et film de polyimide
JP6196731B2 (ja) 新規酸二無水物、この製造方法、及びこれから製造されたポリイミド
KR20170126719A (ko) 신규한 디아민 화합물, 폴리이미드 중합체, 그를 포함하는 폴리이미드 필름 및 그를 이용한 플렉서블 디스플레이용 기판

Legal Events

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

Ref document number: 15740323

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2015740323

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015740323

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15114093

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2016548697

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE