[go: up one dir, main page]

WO2005113647A1 - Polyesterimide de faible coefficient d'expansion thermique lineaire et precurseur de celui-ci - Google Patents

Polyesterimide de faible coefficient d'expansion thermique lineaire et precurseur de celui-ci Download PDF

Info

Publication number
WO2005113647A1
WO2005113647A1 PCT/JP2004/016627 JP2004016627W WO2005113647A1 WO 2005113647 A1 WO2005113647 A1 WO 2005113647A1 JP 2004016627 W JP2004016627 W JP 2004016627W WO 2005113647 A1 WO2005113647 A1 WO 2005113647A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyesterimide
film
precursor
thermal expansion
divalent aromatic
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/JP2004/016627
Other languages
English (en)
Japanese (ja)
Other versions
WO2005113647A6 (fr
Inventor
Masatoshi Hasegawa
Shinsuke Inoue
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.)
Manac Inc
Original Assignee
Manac 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
Application filed by Manac Inc filed Critical Manac Inc
Priority to JP2006513666A priority Critical patent/JP4627297B2/ja
Publication of WO2005113647A1 publication Critical patent/WO2005113647A1/fr
Publication of WO2005113647A6 publication Critical patent/WO2005113647A6/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • C08G73/16—Polyester-imides

Definitions

  • Polyesterimide having low coefficient of linear thermal expansion and its precursor
  • the present invention relates to a practically useful polyester imide and a precursor thereof, which have a low dielectric constant, a low coefficient of linear thermal expansion, a high glass transition temperature, and a sufficient film toughness for use in a flexible printed wiring board. And their manufacturing methods.
  • Polyimide has not only excellent heat resistance but also properties such as chemical resistance, radiation resistance, electrical insulation, and excellent mechanical properties. Currently, it is widely used in various electronic devices as materials, protective films for semiconductor elements, inter-layer insulating films for integrated circuits, and the like.
  • polyimide is prepared by equimolarly dissolving an aromatic tetracarboxylic dianhydride such as pyromellitic anhydride and an aromatic diamine such as diaminodiphenyl ether in an aprotic polar organic solvent such as dimethylacetamide.
  • a polyimide precursor having a high degree of polymerization obtained by the reaction is formed into a film or the like and cured by heating.
  • the skeletal structure In order to maintain the heat resistance of polyimide while applying force, the skeletal structure must be rigid in molecular design, and as a result, many polyimides are insoluble in organic solvents and even at glass transition temperatures or higher. Since it does not melt, it is usually not easy to mold the polyimide itself.
  • a method is used in which a polyimide precursor having high solubility in an amide-based organic solvent is used. Specifically, a polyimide precursor is coated on a metal substrate with a non-tonic organic solvent solution, dried, and heated at 250 ° C to 350 ° C for dehydration ring closure (imidization) to form a polyimide film. I do.
  • polyimides which can also form 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, are best known. It is known that this polyimide film has a very low linear thermal expansion coefficient of 5-lOppmZK, depending on the film thickness and manufacturing conditions (for example, see Non-Patent Documents 2 and 3).
  • introduction of an alicyclic unit into the polyimide skeleton reduces ⁇ electrons, and is effective for lowering the dielectric constant.
  • the introduction of an alicyclic unit generally has a problem in that the linearity and rigidity of the polyimide main chain skeleton are reduced and the coefficient of linear thermal expansion is increased.
  • a highly flexible alicyclic diamine such as 4,4'-methylenebis (cyclohexylamine)
  • polymerization proceeds easily with various acid dianhydrides, and a polyimide precursor having a high degree of polymerization is produced.
  • the polyimide film obtained by the ring closure reaction does not exhibit low thermal expansion characteristics.
  • the obtained polyimide film has a low dielectric constant as described above, but has a linear thermal expansion.
  • the coefficient is as high as 70 ppm ZK, and does not show low thermal expansion characteristics.
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride and polyimide having trans 1,4-sixoxyhexandiamine power have a rigid and relatively linear skeleton, and therefore have a low dielectric constant.
  • the development of low thermal expansion characteristics is expected.
  • the polyimide precursor polymerization reaction of 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 2,2'bis (trifluoromethyl) benzidine the above-mentioned salt formation is suppressed. It does not occur at all and a high molecular weight product can be easily obtained. Furthermore, the polyimide film has a low dielectric constant (2.66), a low thermal expansion coefficient (21PpmZK) and high glass transition temperature (356 ° C) satisfying simultaneously (e.g., Non-Patent Document 5 reference.) 0
  • Non-Patent Document 1 Polymer, 28, 2282 (1987)
  • Non-Patent Document 2 Macromolecules, 29, 7897 (1996)
  • Non-Patent Document 4 Macromolecules, 24, 5001 (1991)
  • Non-Patent Document 5 High Performance Polymers, 15, 47 (2003)
  • Non-Patent Document 6 Macromolecules, 32, 4933 (1999)
  • Non-Patent Document 7 Reactive and Functional Polymers, 30, 61 (1996)
  • the present invention provides a practically useful polyester imide and a precursor thereof, which has a low dielectric constant, a low coefficient of linear thermal expansion, a high glass transition temperature, and also has sufficient film toughness for flexible printed wiring board applications. And a method for producing them.
  • the present invention is as follows.
  • a and B are each independently a divalent aromatic group, an alicyclic group or a combination thereof. However, the bonding positions of the divalent groups are all in the para-position or a relation equivalent thereto.
  • a polyesterimide precursor comprising a repeating unit represented by the formula:
  • [0030] is selected from a divalent aromatic group or an alicyclic group represented by
  • the steric structure of the cyclohexane ring in A and B is the chair-type trans configuration described in 1) above.
  • a and B are each independently a divalent aromatic group, an alicyclic group or a combination thereof. However, the bonding positions of the divalent groups are all in the para-position or a relation equivalent thereto. Polyester imide characterized by containing a repeating unit
  • the polyesterimide as described.
  • the precursor film is subjected to a thermal dehydration cyclization reaction or a cyclization reaction using a dehydration ring closure reagent
  • polyesterimide film according to 8) above which has a dielectric constant lower than 3.3, a linear thermal expansion coefficient lower than 30 ppm ZK, a glass transition temperature of 300 ° C or higher, and sufficient toughness.
  • An electronic device comprising the polyesterimide film described in 8) or 9) above.
  • the present invention focused on ester bonds.
  • Ester bonds are relatively hindered from conformational changes, where the internal rotation barrier is higher than ether bonds, and are expected to provide some degree of flexibility to the main chain.
  • ester bond has a lower polarizability per unit volume than the amide bond or the imide bond
  • introduction of the ester bond into the polyimide is also advantageous for low dielectric constant.
  • ester groups are expected to contribute to a decrease in water absorption, which largely affects the dielectric constant, in view of the fact that polyesters exhibit lower water absorption than polyimide / polyamide.
  • the tetracarboxylic dianhydride monomer used in the production of the polyesterimide of the present invention can be easily synthesized from a diol imparting rigidity or linearity such as hydroquinone and trimellitic anhydride chloride. And the resulting monomer is also of high purity. In addition, the raw materials used can be obtained at low cost, which is advantageous in terms of the production cost of polyesterimide.
  • FIG. 1 is an infrared absorption spectrum of the ester group-containing tetracarboxylic dianhydride described in Example 1.
  • FIG. 2 is an infrared absorption spectrum of the ester group-containing tetracarboxylic dianhydride described in Example 2.
  • FIG. 3 is an infrared absorption spectrum of the polyesterimide precursor film described in Example 3.
  • FIG. 4 is an infrared absorption spectrum of the polyesterimide film described in Example 3.
  • FIG. 5 is an infrared absorption spectrum of the polyesterimide precursor film described in Example 4.
  • FIG. 6 is an infrared absorption spectrum of the polyesterimide film described in Example 4.
  • FIG. 7 is an infrared absorption spectrum of the polyesterimide precursor film described in Example 5.
  • FIG. 8 is an infrared absorption spectrum of the polyesterimide film described in Example 5. BEST MODE FOR CARRYING OUT THE INVENTION
  • the synthesis of the tetracarboxylic dianhydride monomer represented by the formula (3) is performed as follows. First, a diol is dissolved in a dehydrated organic solvent such as tetrahydrofuran or N, N-dimethylformamide, and a tertiary amine such as pyridine / triethylamine is added as a deoxidizing agent. To this solution, a solution of trimellitic anhydride chloride in a molar amount twice as much as that of the diol used was gradually added dropwise while cooling with ice, and the mixture was stirred at room temperature for 24 hours to obtain the desired formula (3):
  • a dehydrated organic solvent such as tetrahydrofuran or N, N-dimethylformamide
  • a tertiary amine such as pyridine / triethylamine
  • A is a divalent aromatic group, an alicyclic group or a combination thereof, provided that the bonding positions of the divalent groups are all in the para-position or a relation equivalent thereto.
  • the tetracarboxylic dianhydride monomer represented can be obtained.
  • the tertiary amine hydrochloride contained in the above reaction solution is removed by filtration, the reaction solvent is distilled off under reduced pressure, and recrystallization is repeated using an appropriate solvent to obtain a high-molecular-weight polymer that can be used for polymerization.
  • a pure ester group-containing acid dianhydride monomer is obtained.
  • the product is dissolved in chloroform and ethyl acetate, and the mixture is shaken with water to extract and remove the hydrochloride salt.
  • the reaction solution into a large amount of water and wash the precipitated product. Since the anhydride groups are partially hydrolyzed by these operations, they are subjected to thermal ring closure at 200 ° C. in vacuum, and finally recrystallized from an appropriate solvent.
  • Ring closure treatment of the ester group-containing tetracarboxylic dianhydride monomer can also be performed by dissolving in a dehydrating agent such as acetic anhydride and heating and refluxing it. When used for applications, it is preferable to thermally close the ring.
  • a dehydrating agent such as acetic anhydride
  • / ⁇ diol is an aromatic or Z or alicyclic dihydroxy compound having two hydroxy groups at each terminal.
  • the bonding positions of the hydroxy group, the aromatic group, and the z or alicyclic group are all related to the para-position or a position corresponding thereto. In charge.
  • the "para position or a relation corresponding thereto" means a relation such that one bonding position is point-symmetric or line-symmetric with respect to the other bonding position.
  • a 6-membered ring such as benzene and cyclohexane means 1,4, and a 10-membered ring such as a naphthalene ring means 2,6 or 1,5.
  • the diol of the present invention is in the para-position or By having a corresponding relationship, a straight and rigid structure is provided.
  • Preferred aromatic dihydroxy conjugates include, specifically, monocyclic and condensed polycyclic carbons having 6 to 24 carbon atoms and having two hydroxyl groups in a para position or a relationship corresponding thereto.
  • Hydrogen groups which may optionally be interconnected directly or by a bridging member (in which case, the two hydroxyl groups are each terminally present).
  • the bridging member is a spacer group having 116 atoms, and may be, for example, alkylene, ONH—, carbonyl, sulfiel, sulfol, or a combination thereof. Further, they may be optionally substituted by one or more halogen, hydroxyl, or alkyl having 14 to 14 carbons, alkyl or alkoxy.
  • More preferable aromatic dihydroxy conjugates include, for example, hydroquinone, 4,4'-biphenol, and 4, A "-dihydroxy-terphenyl.
  • Preferred alicyclic dihydroxy conjugates are, specifically, monocyclic or polycyclic carbons having 6 to 24 carbon atoms having two hydroxyl groups in para-position or a relationship corresponding thereto.
  • Hydrogen groups which may optionally be interconnected directly or by a bridging member (in which case, the two hydroxyl groups are each terminally present).
  • the bridging member is a spacer group having 116 atoms, and may be, for example, alkylene, ONH—, carbol, sulfiel, sulfol, or a combination thereof.
  • More preferred alicyclic dihydroxy conjugates include, for example, trans 1,4-cyclohexanediol.
  • the polymerization of the polyesterimide precursor is performed as follows. First, a diamine component is dissolved in a polymerization solvent, and a tetracarboxylic dianhydride powder represented by the formula (3) is gradually added thereto. Using a mechanical stirrer, 10 to 40 ° C, preferably Stir at room temperature for 0.5-48 hours. At this time, the monomer concentration is 5 to 40% by weight, preferably 10 to 35% by weight. By performing polymerization in this monomer concentration range, a uniform and high polymerization degree polyesterimide precursor solution can be obtained.
  • the polyesterimide precursor of the present invention has an intrinsic viscosity of 0.3 dL / g or more measured in N, N-dimethylacetamide at 30 ° C. at a concentration of 0.5% by weight, and It is preferably in the range of 0.3-6. OdL / g, depending on the desired use of OdL / g.
  • the polyesterimide precursor having a higher degree of polymerization tends to be obtained as the monomer concentration is higher, it is preferable to start the polymerization at the highest possible concentration, particularly for applications where the polyesterimide film requires high toughness.
  • Diamine component is an aromatic and Z or alicyclic diamine compound having two amino groups at the respective terminals.
  • the bonding positions of the amino group, the aromatic group and the Z or alicyclic group are all in the para-position or a relation equivalent thereto.
  • the diamine component of the invention has a linear or rigid structure by having a para-position or a relation equivalent thereto.
  • Preferred diamine components are p-phenylenediamine, benzidine, 4,4 'diaminobenzalide, 1,4 diaminocyclohexane or 4-aminobenzoic acid ⁇ aminophenol, which may be one in some cases. It may be substituted with the above halogen, hydroxyl, or alkyl having 14 to 14 carbon atoms, alkyl halide or alkoxy.
  • 2-methyl-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, benzidine, o-tolidine, m-trizine, 2,2'bis (trifluoromethyl) benzene Gin, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, 4,4'diaminobenzalide, trans 1,4 diaminocyclohexane or 4-aminobenzoic acid 4'-aminophenol are preferred, for example.
  • No. In the polyesterimide according to the present invention, it is preferable to use these diamine components in an amount of 70 to 100% by mole of the diamine components used.
  • the aromatic diamine which can be partially used in the range without significantly impairing the required properties of the polyesterimide according to the present invention is not particularly limited, but m-phenylenediamine, 2,4-diaminotoluene, 2,4 -Diaminoxylene, 2,4-diaminodulene, 4,4'-Diaminodiphenylmethane, 4,4'-Methylenebis (2-methyla-line), 4,4'-Methylenebis (2-ethyla-line), 4,4'-Methylenebis ( 2, 6-dimethyla-phosphine), 4, 4'-methylene bis (2,6-diethyl aniline), 4, 4'-diaminodiphenyl ether, 3, 4'-diaminodidiphenyl ether, 3, 3'-diaminodiphenyl- Diether, 2, 4 '-diaminodiphenyl-ether, 4, 4' diaminodiphenylsulfone, 3, 3 '-d
  • the aliphatic diamine that can be partially used within a range that does not significantly impair the required properties of the polyesterimide is not particularly limited, but cis 1,4-diaminocyclohexane, 1,4-diaminocyclohexane (trans / cis Mixture), 1,3-diaminocyclohexane, isophoronediamine, 1,4-cyclohexanebis (methylamine), 2,5 bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (Aminomethyl) bicyclo [2.2.1] heptane, 3,8 bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 4,4'-methylenebis (cyclohexylamine ), 4,4'-methylenebis (2-methylcyclohexylamine), 4,4'-methylenebis (2-ethylcyclohexylamine), 4,
  • an alicyclic diamine such as 1,4 diaminocyclohexane as the aliphatic diamine.
  • the tetracarboxylic dianhydride represented by the formula (3) according to the present invention When the tetracarboxylic dianhydride represented by the formula (3) according to the present invention is used while reacting, it quickly reacts with trans 1,4-diaminocyclohexane to give a high polymerization degree.
  • a polyesterimide precursor can be easily obtained. Therefore, there is no need for a complicated pre-polymerization treatment step for silylizing aliphatic diamine with a silylating agent such as chlorotrimethylsilane.
  • a diamine containing an ester bond such as 4-aminobenzoic acid 4′-aminophenol is used as the aromatic diamine. It is also preferable to use the
  • An acid dianhydride component other than the tetracarboxylic dianhydride represented by the formula (3) is partially added to the polyesterimide according to the present invention in a range not significantly impairing the required properties and polymerization reactivity.
  • the copolymeric dianhydride component is not particularly limited, but may be pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4 ' Benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4'-biphenyl ether tetracarboxylic dianhydride, 3, 3', 4, 4'-biphenyl sulfone tetracarboxylic dianhydride 2,2'bis (3,4-dicarboxyphenyl) hexafluoropropanoic dianhydride, 2,2'bis (3,4-dicarboxyphenyl) propanoic dianhydride, Examples include 1,4,5,8-naphthalenetetracarboxylic dianhydride. These may be used alone or in combination of two or more as copolymer components.
  • a polymer dissolution promoter often added during the polymerization of the polyesterimide precursor that is, a metal salt such as lithium bromide / lithium chloride, need not be used at all in the polyesterimide precursor polymerization reaction according to the present invention. ,. These metal salts should not be used because even if trace amounts of metal ions remain in the polyesterimide film, the reliability as an electronic device is significantly reduced.
  • the polyesterimide precursor solution applied on the substrate is dried in a range of 40 ° C to 180 ° C.
  • the obtained polyesterimide precursor film is heat-treated on a substrate in air, in an atmosphere of an inert gas such as nitrogen, or in a vacuum, at a temperature of 200 ° C to 430 ° C, preferably 250 ° C to 400 ° C.
  • an inert gas such as nitrogen
  • a vacuum at a temperature of 200 ° C to 430 ° C, preferably 250 ° C to 400 ° C.
  • Imido-dani can also be performed chemically using a dehydration cyclization reagent. That is, a polyesterimide film can also be obtained by immersing the polyesterimide precursor film formed on the substrate in acetic anhydride containing a basic catalyst such as pyridine or triethylamine at room temperature for one minute and several hours.
  • a basic catalyst such as pyridine or triethylamine
  • additives such as an acid stabilizer, a terminal blocking agent, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer may be added, if necessary. May be mixed.
  • a 0.5% by weight solution of the polyesterimide precursor in N, N-dimethylacetamide was measured at 30 ° C. using an Ostwald viscometer.
  • the dynamic viscoelasticity was measured from the loss peak at a frequency of 0.1 ⁇ and a heating rate of 5 ° CZ.
  • thermogravimetric change of the polyesterimide film was measured at a heating rate of 10 ° CZ, and the temperature at which the weight was reduced by 5% was determined.
  • the coefficient of linear thermal expansion was determined as the average value in the range of 100 to 200 ° C from the elongation of the test piece at a load of 0.5 gZ, a film thickness of 1 ⁇ m, and a heating rate of 5 ° CZ.
  • the dielectric constant and the dielectric loss tangent were measured by preparing an electrode pattern by depositing gold on a polyesterimide film cut into a circular shape with a diameter of 5 cm, and sandwiching it with a dielectric measurement electrode 16451B manufactured by Agilent Technologies, Inc. The measurement was performed at a relative humidity of 46% by connecting to a high-precision LCR meter 4285A manufactured by Technology One.
  • polyesterimide film was vacuum-dried at 50 ° C for 24 hours, immersed in water at 25 ° C for 24 hours, and calculated as an increase in weight after wiping off excess water.
  • the Young's modulus, breaking strength and breaking elongation of the polyesterimide film were determined by performing a tensile test on a 30 mm ⁇ 3 mm test piece using Tensilon manufactured by Toyo Baldwin Co. at a tensile speed of 8 mmZ.
  • the reaction solution was concentrated by an evaporator and dropped into water to obtain a precipitate.
  • the ring is partially hydrolyzed and the ring is opened.
  • the crude product obtained for ring closing is vacuum-dried at 200 ° C for 24 hours. It was recrystallized from (volume ratio 8Z2). The crystals separated by filtration were further dried in vacuum at 200 ° C. for 24 hours. From the infrared absorption spectrum (FIG. 1), it was confirmed that the target tetracarboxylic dianhydride was obtained, and that the thermal ring closure was completely performed.
  • the polyesterimide precursor solution did not precipitate or gel at all even when left at room temperature and 20 ° C for one month, and showed extremely high solution storage stability.
  • the intrinsic viscosity of the polyesterimide precursor measured with an Ostwald viscometer in N, N-dimethylacetamide at 30 ° C. at a concentration of 0.5% by weight was 1.12 dLZg.
  • polyesterimide precursor solution was applied to a glass substrate, and dried at 60 ° C for 2 hours.
  • the resulting polyesterimide precursor film was thermally imidized on the substrate at 250 ° C under reduced pressure for 2 hours. After that, the substrate force was removed to remove residual stress, and heat treatment was further performed at 350 ° C for 1 hour to obtain a transparent polyesterimide film having a thickness of 20 m.
  • the polyesterimide film did not break even in the 180 ° bending test, and showed toughness.
  • the polymer did not show any solubility in any organic solvent.
  • this polyesterimide film As a result of dynamic viscoelasticity measurement of this polyesterimide film, no clear glass transition point (determined from the loss peak in the dynamic viscoelasticity curve) was observed, and a force showing no thermoplasticity was observed. . This shows that this polyesterimide film is extremely high and has dimensional stability.
  • the dielectric constant estimated from the average refractive index is 3.26, a typical wholly aromatic low thermal expansion polyesterimide composed of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and ⁇ -phenylenediamine. It was lower than the dielectric constant (3.5). This result is the effect of introducing an ester group into the polyesterimide skeleton.
  • the 5% weight loss temperature was 470 ° C in nitrogen and 463 ° C in air.
  • this Polyester Luimide exhibited a very low coefficient of linear thermal expansion, excellent dimensional stability, high thermal stability, and sufficient film toughness.
  • the infrared absorption spectra of the obtained polyesterimide precursor film and polyesterimide film are shown in FIGS. 3 and 4, respectively.
  • the polyesterimide precursor solution was applied to a glass substrate, and dried at 60 ° C for 2 hours.
  • a polyesterimide precursor film obtained was thermally imidized on the substrate at 250 ° C under reduced pressure for 2 hours. After that, the substrate force was removed to remove residual stress, and heat treatment was further performed at 350 ° C for 1 hour to obtain a transparent polyesterimide film having a thickness of 20 m.
  • the polyesterimide film did not break even in the 180 ° bending test, and showed toughness.
  • the polymer did not show any solubility in any organic solvent.
  • the dielectric constant estimated from the average refractive index is 3.22, a semi-aromatic low thermal expansion polyester which has 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 1,4-cyclohexanediamine. Comparable with the dielectric constant of imide (3.15) Value.
  • the 5% weight loss temperature was 481 ° C in nitrogen and 463 ° C in air.
  • the polyesterimide exhibited a coefficient of linear thermal expansion as low as silicon, excellent dimensional stability, high thermal stability, and sufficient film toughness.
  • the infrared absorption spectra of the obtained polyesterimide precursor film and polyesterimide film are shown in FIGS. 5 and 6, respectively.
  • polymerization was conducted from 2,2′bis (trifluoromethyl) benzidine and the tetracarboxylic dianhydride described in Example 2 to obtain a transparent, uniform and viscous polyesterimide precursor. A body solution was obtained.
  • the polyesterimide precursor solution did not precipitate or gel at all even when left at room temperature and 20 ° C for one month, and showed extremely high solution storage stability.
  • the intrinsic viscosity of the polyesterimide precursor measured with an Ostwald viscometer at 30 ° C. and 0.5% by weight in N, N-dimethylacetamide was 2.93 dLZg, which was an extremely high molecular weight substance.
  • This polyesterimide precursor solution was applied to a glass substrate, and dried at 60 ° C for 2 hours.
  • the resulting polyesterimide precursor film was thermally imidized on the substrate at 250 ° C under reduced pressure for 2 hours. After that, the substrate force was removed to remove residual stress, and heat treatment was further performed at 350 ° C for 1 hour to obtain a transparent polyesterimide film having a thickness of 20 m.
  • the polyesterimide film did not break even in the 180 ° bending test, and showed toughness.
  • the glass transition temperature was 360 ° C or higher.
  • the dielectric constant estimated from the average refractive index was relatively low at 2.99.
  • the 5% weight loss temperature was 487 ° C in nitrogen and 479 ° C in air.
  • FIGS. 7 and 8 show infrared absorption spectra of the obtained polyesterimide precursor film and polyesterimide film, respectively.
  • Example 6 According to the method described in Example 4, polymerization was carried out from trans 1,4-diaminocyclohexane and the tetracarboxylic dianhydride described in Example 2. Although a salt was formed in the early stage of the polymerization, the salt was not so strong and was gradually dissolved by stirring, and after 24 hours, a clear, uniform and viscous polyesterimide precursor solution was obtained. This polyesterimide precursor solution did not precipitate or gel at all even when left at room temperature and 20 ° C. for one month, and showed extremely high solution storage stability. The intrinsic viscosity of the polyesterimide precursor measured in an N, N-dimethylacetamide at 30 ° C. and a concentration of 0.5% by weight with an Ostwald viscometer was 0.52 dLZg. Casting and thermal imidation were performed according to the method described in Example 4 to obtain a polyesterimide film having high transparency.
  • Example 4 According to the method described in Example 4 except that N-methyl-2-pyrrolidone was used instead of N, N-dimethylacetamidoamide as the polymerization solvent, trans 1,4-diaminocyclohexane and described in Example 2 were used.
  • N-methyl-2-pyrrolidone was used instead of N, N-dimethylacetamidoamide as the polymerization solvent
  • trans 1,4-diaminocyclohexane and described in Example 2 were used.
  • the polyesterimide precursor solution did not precipitate or gel at all even when left at room temperature and 20 ° C for one month, and showed extremely high solution storage stability.
  • the intrinsic viscosity of the polyester imide precursor measured with an Ostwald viscometer at 30 ° C. and 0.5% by weight in N, N dimethylacetamide was 1.14 dLZg, which was a high molecular weight product.
  • polyesterimide precursor solution was applied to a glass substrate and dried at 60 ° C for 2 hours.
  • the obtained polyesterimide precursor film was placed on the substrate at 250 ° C under reduced pressure for 1 hour and further at 300 ° C. After performing thermal imidation for 1 hour, the substrate was peeled off to remove residual stress, and heat treatment was further performed at 350 ° C for 1 hour to obtain a highly transparent polyesterimide film having a thickness of 20 m.
  • polyesterimide film did not break even in the 180 ° bending test, and showed toughness.
  • the 5% weight loss temperature was 471 ° C in nitrogen and 428 ° C in air.
  • the polyesterimide exhibited a low coefficient of linear thermal expansion near copper substrates, a high glass transition temperature, a very high Young's modulus, a relatively low dielectric constant, high thermal stability, and good film toughness.
  • polymerization was carried out using 4,4 ′ diaminobenzalide and the tetracarboxylic dianhydride described in Example 2 to obtain a transparent, uniform and viscous polyester imid. A precursor solution was obtained.
  • polyesterimide precursor solution did not precipitate or gel at all even when left at room temperature and 20 ° C for one month, and showed extremely high solution storage stability.
  • the intrinsic viscosity of the polyesterimide precursor measured with an Ostwald viscometer at 30 ° C. and 0.5% by weight in N, N-dimethylacetamide was 2.37 dLZg, which was an extremely high molecular weight substance.
  • polyesterimide precursor solution was applied to a glass substrate and dried at 60 ° C for 2 hours.
  • the obtained polyesterimide precursor film was placed on the substrate at 250 ° C under reduced pressure for 1 hour and further at 300 ° C. After performing thermal imidation for 1 hour, the substrate was peeled off to remove residual stress, and heat treatment was further performed at 350 ° C. for 1 hour to obtain a transparent polyesterimide film having a thickness of 20 m.
  • polyesterimide film did not break even in the 180 ° bending test, and showed toughness.
  • polyesterimide film has extremely high dimensional stability.
  • the dielectric constant estimated from the average refractive index was 3.26, and the water absorption was 2.06%.
  • the 5% weight loss temperature was 480 ° C in nitrogen and 470 ° C in air.
  • the metal exhibited a very low coefficient of linear thermal expansion, high glass transition temperature, relatively low dielectric constant, high thermal stability, and good film toughness.
  • 4-Aminobenzoic acid 4'-aminofurol (APAB) lOmmol is placed in a well-dried closed reaction vessel with a stirrer, dissolved in N, N-dimethylacetamide sufficiently dehydrated with molecular sieves 4A, and then dissolved in this solution. Then, 10 mmol of the tetracarboxylic dianhydride powder described in Example 2 was gradually dried. The mixture was stirred at room temperature for 48 hours while appropriately diluting with the same solvent to obtain a transparent, uniform and viscous polyesterimide precursor solution.
  • APAB 4-Aminobenzoic acid 4'-aminofurol
  • polyesterimide precursor solution did not precipitate or gel at all even when left at room temperature and 20 ° C. for one month, and showed extremely high solution storage stability.
  • the intrinsic viscosity of the polyesterimide precursor measured in an N, N-dimethylacetamide at 30 ° C. and a concentration of 0.5% by weight with an Ostwald viscometer was 2.81 dLZg, which was an extremely high polymer.
  • the polyesterimide precursor solution was applied to a glass substrate and dried at 60 ° C. for 1 hour.
  • the polyesterimide precursor film obtained was dried on the substrate at 250 ° C. under reduced pressure for 1 hour and further at 300 ° C.
  • a final heat treatment was performed at 350 ° C for 1 hour to obtain a transparent polyesterimide film having a film thickness of 20 ⁇ m.
  • polyesterimide film did not break even in the 180 ° bending test, and showed toughness.
  • the dielectric constant measured at a frequency of 1 MHz with a high-precision LCR meter was 3.22, which was close to the dielectric constant 3.26 estimated from the average refractive index.
  • the dielectric loss tangent was 0.025, which was a relatively low value.
  • the Young's modulus was 7.1 lGPa and the breaking strength was 0.22 GPa, which was extremely high elasticity and high strength, and the breaking elongation was 11%.
  • the 5% weight loss temperature was 471 ° C in nitrogen and 452 ° C in air.
  • the polyesterimide has a relatively low dielectric constant and And a very low coefficient of linear thermal expansion comparable to that of a silicon substrate, a very high Young's modulus, and a very low water absorption, and had sufficient film toughness.
  • polyesterimide precursor solution did not precipitate or gel at all even when left at room temperature and 20 ° C. for one month, and showed extremely high solution storage stability.
  • the intrinsic viscosity of the polyesterimide precursor measured with an Ostwald viscometer at 30 ° C. and 0.5% by weight in N, N-dimethylacetamide was 1.08 dLZg, which was a high polymer.
  • the polyesterimide precursor solution was applied to a glass substrate, and dried at 60 ° C for 1 hour.
  • the resulting polyesterimide precursor film was placed on the substrate at 250 ° C under reduced pressure for 1 hour and further at 300 ° C.
  • a final heat treatment was performed at 350 ° C for 1 hour to obtain a transparent polyesterimide film having a film thickness of 20 ⁇ m.
  • polyesterimide film did not break even in the 180 ° bending test, and showed toughness.
  • the glass transition point was 395 ° C.
  • the storage elastic modulus of the polyesterimide film was hardly reduced, indicating that the dimensional stability was high!
  • the water absorption was 0.66%, an extremely low value.
  • the dielectric constant estimated from the average refractive index was 3.20.
  • the Young's modulus was 6.28 GPa and the breaking strength was 0.295 GPa, which was extremely high elasticity and strength, and the breaking elongation was 36%.
  • the 5% weight loss temperature was 487 ° C in nitrogen and 485 ° C in air.
  • the present polyesterimide has a relatively low dielectric constant, a low linear thermal expansion coefficient almost equal to that of a copper substrate, and an extremely high dielectric constant. It exhibited a high glass transition temperature, a very high Young's modulus and a very low water absorption, and had sufficient film toughness.
  • An ester group-containing tetracarboxylic dianhydride was synthesized from 2,2′-biphenol and twice the molar amount of trimellitic anhydride chloride. This is the isomer of the tetracarboxylic dianhydride described in Example 1. From this acid dianhydride and p-phenylenediamine, a polyesterimide precursor was polymerized according to the methods shown in Examples 3 and 4. The intrinsic viscosity of the polyesterimide precursor measured in an N, N-dimethylacetamide at 30 ° C. and a concentration of 0.5% by weight with a Ostwald viscometer was 0.53 dLZg.
  • polyesterimide precursor solution was applied to a glass substrate, and dried at 60 ° C for 2 hours.
  • the obtained polyesterimide precursor film was thermally imidized at 300 ° C for 1 hour under reduced pressure on the substrate.
  • a transparent and tough polyesterimide film with a thickness of 20 m was obtained.
  • the linear thermal expansion coefficient of this polyesterimide film was as high as 66 ppmZK, and the required characteristics according to the present invention were satisfied. This is because the benzene rings are greatly twisted due to steric hindrance that cannot be caused by the 2,2'-biphenyl bond force in the acid dianhydride and the S-para bond. This is because spontaneous in-plane orientation was hardly induced.
  • the polyesterimide of the present invention has a low dielectric constant, a low coefficient of linear thermal expansion, a high glass transition temperature, and a sufficient film toughness. In addition to these, it preferably has a low water absorption. Since they can be held together, as precision electronic materials, for example, electronic devices such as flexible printed wiring boards, cover materials (protective films) for electronic circuits on flexible printed wiring boards, protective films for semiconductor devices, or interlayer insulating films for integrated circuits, In particular, it is suitable for use on flexible printed wiring boards.
  • the polyesterimide film of the present invention is laminated with a laminate, for example, amorphous silicon, by utilizing an extremely low linear thermal expansion coefficient comparable to that of a copper substrate or a silicon substrate as described in Example 410. It is also useful to use it as a base film for solar cells.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (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

Il est prévu un polyesterimide très utile dans la pratique, de faible permittivité, de faible coefficient d’expansion thermique linéaire et de température élevée de transition vitreuse, avec une résistance de film suffisante pour les cartes imprimées souples ; un précurseur pour le polyesterimide ; et un procédé de production de ceux-ci. Le polyesterimide est caractérisé en ce qu’il contient des unités répétées représentées par la formule (2): où A et B représentent chacun indépendamment un groupe aromatique ou alicyclique divalent ou bien une combinaison de ceux-ci, sous réserve qu’à la fois dans A et B, les deux liaisons effectuées avec les atomes adjacents présentent un para-agencement ou un agencement équivalent à celui-ci.
PCT/JP2004/016627 2004-05-21 2004-11-10 Polyesterimide de faible coefficient d'expansion thermique lineaire et precurseur de celui-ci Ceased WO2005113647A6 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006513666A JP4627297B2 (ja) 2004-05-21 2004-11-10 低線熱膨張係数を有するポリエステルイミドとその前駆体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004152406 2004-05-21
JP2004-152406 2004-05-21

Publications (2)

Publication Number Publication Date
WO2005113647A1 true WO2005113647A1 (fr) 2005-12-01
WO2005113647A6 WO2005113647A6 (fr) 2005-12-01

Family

ID=

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007314443A (ja) * 2006-05-24 2007-12-06 Manac Inc エステル基含有テトラカルボン酸化合物、ポリエステルイミド前駆体、ポリエステルイミドおよびこれらの製造方法
WO2008091011A1 (fr) * 2007-01-26 2008-07-31 Honshu Chemical Industry Co., Ltd. Nouveau dianhydride d'acide tétracarboxylique à teneur en groupe ester, nouveau précurseur de polyesterimide dérivé de celui-ci et polyesterimide
WO2009139086A1 (fr) * 2008-05-16 2009-11-19 旭化成イーマテリアルズ株式会社 Précurseur de polyester-imide et polyester-imide
JP2009275183A (ja) * 2008-05-16 2009-11-26 Asahi Kasei E-Materials Corp ポリアミド酸ワニス組成物及びそれを用いた金属ポリイミド複合体
JP2010047674A (ja) * 2008-08-20 2010-03-04 Asahi Kasei E-Materials Corp ポリエステルイミド前駆体及びポリエステルイミド
JP2011063647A (ja) * 2009-09-15 2011-03-31 Asahi Kasei E-Materials Corp ポリイミドフィルム及びポリイミド金属積層板
JP2017179000A (ja) * 2016-03-28 2017-10-05 株式会社カネカ ポリアミド酸、ポリイミド、ポリアミド酸溶液、およびポリイミドの利用
WO2021085284A1 (fr) * 2019-10-31 2021-05-06 住友化学株式会社 Film optique et dispositif d'affichage souple
JP2021075701A (ja) * 2019-10-31 2021-05-20 住友化学株式会社 光学フィルム及びフレキシブル表示装置
CN113402882A (zh) * 2015-02-10 2021-09-17 日产化学工业株式会社 剥离层形成用组合物
JP2021147544A (ja) * 2020-03-19 2021-09-27 住友ベークライト株式会社 ポリヒドロキシイミド、ポリマー溶液、感光性樹脂組成物およびその用途
JP2021152634A (ja) * 2020-03-19 2021-09-30 住友ベークライト株式会社 ネガ型感光性樹脂組成物、ネガ型感光性ポリマー及びその用途
KR20210131899A (ko) 2020-04-24 2021-11-03 아사히 가세이 가부시키가이샤 폴리이미드 전구체 및 그것을 포함하는 수지 조성물, 폴리이미드 수지막, 수지 필름 및 그 제조 방법
CN115151977A (zh) * 2020-03-03 2022-10-04 昭和电工材料株式会社 聚酰亚胺前体、树脂组合物、绝缘电线及柔性基板
KR20230147181A (ko) 2021-04-02 2023-10-20 아사히 가세이 가부시키가이샤 폴리이미드, 수지 조성물, 폴리이미드 필름, 및, 그 제조 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS435911B1 (fr) * 1964-03-03 1968-03-04
JPS4890395A (fr) * 1972-03-07 1973-11-26
US5322920A (en) * 1990-07-25 1994-06-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Thermosetting esterimide oligomer and its production method
US5668247A (en) * 1992-12-16 1997-09-16 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Thermoplastic polyimide, polyamide acid, and thermally fusible laminated film for covering conductive wires
JP2004079826A (ja) * 2002-08-20 2004-03-11 Nippon Steel Chem Co Ltd 配線基板用積層体
JP2004082495A (ja) * 2002-08-27 2004-03-18 Kanegafuchi Chem Ind Co Ltd 視認性に優れた耐熱性フレキシブル銅張積層板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS435911B1 (fr) * 1964-03-03 1968-03-04
JPS4890395A (fr) * 1972-03-07 1973-11-26
US5322920A (en) * 1990-07-25 1994-06-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Thermosetting esterimide oligomer and its production method
US5668247A (en) * 1992-12-16 1997-09-16 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Thermoplastic polyimide, polyamide acid, and thermally fusible laminated film for covering conductive wires
JP2004079826A (ja) * 2002-08-20 2004-03-11 Nippon Steel Chem Co Ltd 配線基板用積層体
JP2004082495A (ja) * 2002-08-27 2004-03-18 Kanegafuchi Chem Ind Co Ltd 視認性に優れた耐熱性フレキシブル銅張積層板

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007314443A (ja) * 2006-05-24 2007-12-06 Manac Inc エステル基含有テトラカルボン酸化合物、ポリエステルイミド前駆体、ポリエステルイミドおよびこれらの製造方法
WO2008091011A1 (fr) * 2007-01-26 2008-07-31 Honshu Chemical Industry Co., Ltd. Nouveau dianhydride d'acide tétracarboxylique à teneur en groupe ester, nouveau précurseur de polyesterimide dérivé de celui-ci et polyesterimide
JP2014001394A (ja) * 2007-01-26 2014-01-09 Honshu Chem Ind Co Ltd 新規なエステル基含有テトラカルボン酸二無水物類、それから誘導される新規なポリエステルイミド前駆体及びポリエステルイミド
JP5491735B2 (ja) * 2007-01-26 2014-05-14 本州化学工業株式会社 新規なエステル基含有テトラカルボン酸二無水物類、それから誘導される新規なポリエステルイミド前駆体及びポリエステルイミド
WO2009139086A1 (fr) * 2008-05-16 2009-11-19 旭化成イーマテリアルズ株式会社 Précurseur de polyester-imide et polyester-imide
JP2009275183A (ja) * 2008-05-16 2009-11-26 Asahi Kasei E-Materials Corp ポリアミド酸ワニス組成物及びそれを用いた金属ポリイミド複合体
JP2010047674A (ja) * 2008-08-20 2010-03-04 Asahi Kasei E-Materials Corp ポリエステルイミド前駆体及びポリエステルイミド
JP2011063647A (ja) * 2009-09-15 2011-03-31 Asahi Kasei E-Materials Corp ポリイミドフィルム及びポリイミド金属積層板
CN113402882A (zh) * 2015-02-10 2021-09-17 日产化学工业株式会社 剥离层形成用组合物
CN113402882B (zh) * 2015-02-10 2024-02-06 日产化学工业株式会社 剥离层形成用组合物
JP2017179000A (ja) * 2016-03-28 2017-10-05 株式会社カネカ ポリアミド酸、ポリイミド、ポリアミド酸溶液、およびポリイミドの利用
JP2021075701A (ja) * 2019-10-31 2021-05-20 住友化学株式会社 光学フィルム及びフレキシブル表示装置
CN114599739A (zh) * 2019-10-31 2022-06-07 住友化学株式会社 光学膜和柔性显示装置
WO2021085284A1 (fr) * 2019-10-31 2021-05-06 住友化学株式会社 Film optique et dispositif d'affichage souple
JP7623817B2 (ja) 2019-10-31 2025-01-29 住友化学株式会社 光学フィルム及びフレキシブル表示装置
CN115151977A (zh) * 2020-03-03 2022-10-04 昭和电工材料株式会社 聚酰亚胺前体、树脂组合物、绝缘电线及柔性基板
JP2021147544A (ja) * 2020-03-19 2021-09-27 住友ベークライト株式会社 ポリヒドロキシイミド、ポリマー溶液、感光性樹脂組成物およびその用途
JP2021152634A (ja) * 2020-03-19 2021-09-30 住友ベークライト株式会社 ネガ型感光性樹脂組成物、ネガ型感光性ポリマー及びその用途
JP7435110B2 (ja) 2020-03-19 2024-02-21 住友ベークライト株式会社 ポリヒドロキシイミド、ポリマー溶液、感光性樹脂組成物およびその用途
JP7556263B2 (ja) 2020-03-19 2024-09-26 住友ベークライト株式会社 ネガ型感光性樹脂組成物、ネガ型感光性ポリマー及びその用途
KR20210131899A (ko) 2020-04-24 2021-11-03 아사히 가세이 가부시키가이샤 폴리이미드 전구체 및 그것을 포함하는 수지 조성물, 폴리이미드 수지막, 수지 필름 및 그 제조 방법
KR20230147181A (ko) 2021-04-02 2023-10-20 아사히 가세이 가부시키가이샤 폴리이미드, 수지 조성물, 폴리이미드 필름, 및, 그 제조 방법

Also Published As

Publication number Publication date
JP4627297B2 (ja) 2011-02-09
TW200538489A (en) 2005-12-01
TWI344967B (en) 2011-07-11
JPWO2005113647A1 (ja) 2008-03-27

Similar Documents

Publication Publication Date Title
JP5491735B2 (ja) 新規なエステル基含有テトラカルボン酸二無水物類、それから誘導される新規なポリエステルイミド前駆体及びポリエステルイミド
JP5727795B2 (ja) エステル基含有テトラカルボン酸二無水物、ポリエステルポリイミド前駆体、ポリエステルイミドおよびこれらの製造方法
JP4868183B2 (ja) 新規なフッ素化テトラカルボン酸二無水物、これより得られるポリイミド前駆体、ポリイミドとその利用
JP2009286854A (ja) ポリエステルイミド前駆体およびポリエステルイミド
JP2008001876A (ja) ポリエステルイミドおよびその製造方法
JP4815690B2 (ja) ポリイミド、ポリイミド前駆体及びこれらの製造方法
WO2009139086A1 (fr) Précurseur de polyester-imide et polyester-imide
EP2295489A1 (fr) Précurseur de polyimide linéaire, polyimide linéaire, produit durci à chaud du polyimide linéaire et procédé de fabrication du polyimide linéaire
JP3934335B2 (ja) ポリイミドおよびその製造方法
JP3859984B2 (ja) ポリイミドおよびその製造方法
JP4788108B2 (ja) 低誘電率、低線熱膨張係数、高透明性、高ガラス転移温度を併せ持つポリイミドとその前駆体
JP4918025B2 (ja) エステル基含有テトラカルボン酸二無水物、ポリエステルポリイミド前駆体、ポリエステルイミドおよびこれらの製造方法
JP4699321B2 (ja) エステル基含有ポリイミド、その前駆体及びこれらの製造方法
EP2145910A1 (fr) Précurseur de polyimide linéaire ayant une structure asymétrique, polyimide et procédés de production de ceux-ci
JP2009286853A (ja) ポリエステルイミド前駆体およびポリエステルイミド
JP5244303B2 (ja) ポリエステルイミドおよびその製造方法
JP2011148901A (ja) リン含有ジアミンおよびこれより得られるリン含有ポリイミド
JP4627297B2 (ja) 低線熱膨張係数を有するポリエステルイミドとその前駆体
JP4792204B2 (ja) 高い有機溶媒溶解性、高熱可塑性、高靭性および高ガラス転移温度を併せ持つポリイミド、およびその製造方法
JP7621923B2 (ja) テトラカルボン酸二無水物、ポリエステルイミド前駆体およびその製造方法、ならびに、ポリエステルイミドおよびその製造方法
JPWO2005113647A6 (ja) 低線熱膨張係数を有するポリエステルイミドとその前駆体
JP4957077B2 (ja) テトラカルボン酸類またはこれらから誘導されるポリエステルイミド及びその製造方法
JP4603929B2 (ja) エステルイミドオリゴマー、その熱硬化物およびこれらの製造方法
JP2008163090A (ja) テトラカルボン酸二無水物およびその製造方法並びに重合物
JP3907549B2 (ja) ワニスおよび架橋ポリイミド

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006513666

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase