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WO2012033115A1 - Matière à base de polyimide multi-ramifié, film résistant à la chaleur et procédé de production d'un film à base de polyimide multi-ramifié - Google Patents

Matière à base de polyimide multi-ramifié, film résistant à la chaleur et procédé de production d'un film à base de polyimide multi-ramifié Download PDF

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WO2012033115A1
WO2012033115A1 PCT/JP2011/070330 JP2011070330W WO2012033115A1 WO 2012033115 A1 WO2012033115 A1 WO 2012033115A1 JP 2011070330 W JP2011070330 W JP 2011070330W WO 2012033115 A1 WO2012033115 A1 WO 2012033115A1
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Prior art keywords
film
polyimide
branched
stretching
polyamic acid
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English (en)
Japanese (ja)
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山田　保治
酒井　純
俊輔 谷江
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Ibiden Co Ltd
Kyoto Institute of Technology NUC
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Ibiden Co Ltd
Kyoto Institute of Technology NUC
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • 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 multibranched polyimide-based material, a heat-resistant film, and a method for producing a multibranched polyimide-based film, and is particularly used for an interlayer insulating film or a protective film of a semiconductor element, various electronic devices, solar cells, or the like.
  • the present invention relates to a multi-branched polyimide material used for a base film or a coverlay of a flexible printed wiring board.
  • Polyimide has been used for various applications since it has excellent heat resistance and electrical insulation, chemical resistance, radiation resistance and mechanical properties. In particular, in recent years, it has been widely used for various electronic components. Specifically, a film-like polyimide is used as an interlayer insulating film or a protective film in a semiconductor element. In addition, polyimides having various compositions are used as constituent materials for base films or coverlays of flexible printed wiring boards employed in various electronic devices or solar cells.
  • the dimensional stability in each of the polyimide film and the semiconductor element is about the same, more specifically, the coefficient of linear thermal expansion (CTE) in each of the polyimide film and the semiconductor element. It is said that it is important to make the values comparable. This is because, for example, even when a temperature change occurs in an adherend (semiconductor element) covered with a protective film made of a polyimide film, the interface stress accompanying the temperature change of the adherend (the interface between the polyimide film and the semiconductor element) This is because the generation of stress) can be suppressed as much as possible, and cracking or peeling of the polyimide film can be prevented.
  • CTE coefficient of linear thermal expansion
  • Patent Document 1 International Publication No. 2005/113647
  • a polyesterimide precursor characterized by containing a repeating unit represented by a predetermined chemical formula has been proposed.
  • Patent Document 2 Japanese Patent Laid-Open No. 2009-67042
  • a solvent solution of a polyimide precursor is cast on a support, the solvent in the solvent solution is removed, and the film is peeled from the support as a self-supporting film.
  • a method for producing a polyimide film has been proposed in which a self-supporting film is stretched in the width direction at an initial heating temperature of 80 to 300 ° C. and then heated at a final heating temperature of 350 to 580 ° C.
  • the stretch ratio of the self-supporting film in the production method of Patent Document 2 is preferably 1.01 to 1.12 times.
  • the draw ratio in Patent Document 2 is A in the width direction after stretching, and the width direction before stretching.
  • the length is B, it is calculated from the formula: (AB) / B.
  • draw ratio in the following description and claims of the present application, It is synonymous with what is calculated from a formula.
  • Patent Document 3 Japanese Patent Laid-Open No. 8-174659
  • a TAB composed of a base film layer, an adhesive layer, and a protective layer used in a TAB (Tape Automated Automated Bonding) method which is one of IC mounting techniques.
  • a base film layer a tape obtained by stretching a polyimide film in a uniaxial direction at a stretch ratio of 10 to 100% under heating has been proposed.
  • Patent Document 4 Japanese Patent No. 2999116 proposes a branched polyimide represented by a repeating unit represented by a predetermined chemical formula.
  • the branched polyimide is one in which a slightly multi-branched portion is introduced into a linear polyimide, and is equivalent to that at the time of melt molding such as extrusion molding as compared with a conventional linear polyimide having the same molecular weight. It is described that it exhibits a melt viscosity and an equivalent raw film can be obtained, and that further uniform stretching is possible.
  • the coefficient of linear thermal expansion is in a range lower than 15 ppm / ° C.
  • the composition of the controllable resin is limited, and many of the resins require large stretching, specifically, stretching treatment with a stretching ratio of 1 or more. The reason is that the molecular orientation generated by the stretching process with a large stretching ratio does not disappear even by the heat treatment (annealing process) after the stretching process, and the stretching effect can be maintained.
  • the present invention has been made in the background of such circumstances, and the problem to be solved is a multi-branched polyimide material exhibiting excellent dimensional stability as well as excellent mechanical properties, heat resistance It is providing the manufacturing method of a film and a multi-branch polyimide film.
  • the present invention has an average linear thermal expansion coefficient at 50 to 250 ° C. obtained by polymerizing pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene.
  • the gist of the present invention is a multi-branched polyimide material composed of a multi-branched polyimide at ⁇ 1.0 to 28.0 ppm / ° C.
  • the multibranched polyimide material preferably, is an intermediate reaction product of pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene.
  • a film made of a certain multi-branched polyamic acid is subjected to a stretching treatment with a draw ratio of 0.05 to 0.50 times and an imidization treatment. In this case, the average linear thermal expansion coefficient is measured in the same direction as the stretching direction.
  • the gist of the present invention is also a heat-resistant film made of the multi-branched polyimide material of each aspect described above.
  • pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene are polymerized to form a film made of multibranched polyamic acid, and a film made of the multibranched polyamic acid
  • the gist of the present invention is also a method for producing a multi-branched polyimide film characterized by being subjected to stretching treatment and imidization treatment so that the stretching ratio is 0.05 to 0.50 times.
  • multi-branched polyimide material In the multi-branched polyimide material according to the present invention, average linear thermal expansion at 50 to 250 ° C. obtained by dehydration condensation of pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene Since it is made of a specific multi-branched polyimide having a low coefficient of -1.0 to 28.0 ppm / ° C, it can exhibit excellent dimensional stability as well as excellent mechanical properties.
  • the multibranched polyimide material according to the present invention is stable after heat treatment at about 250 ° C., a specific multibranch having a low average linear thermal expansion coefficient of ⁇ 1.0 to 28.0 ppm / ° C. Since it consists of polyimide, it can exhibit excellent dimensional stability as well as excellent mechanical properties.
  • the above-mentioned multibranched polyimide is particularly suitable for a film composed of a multibranched polyamic acid that is an intermediate reaction product of pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene.
  • Is obtained by performing imidization by appropriately setting the stretching ratio within the above range when the film is subjected to a stretching treatment and imidization treatment of 0.05 to 0.50 times The average linear thermal expansion coefficient at 50 to 250 ° C. can be set to a desired value within the range of ⁇ 1.0 to 28.0 ppm / ° C., and a desired multi-branched polyimide material can be obtained. it can.
  • FIG. 3 is a diagram showing TMA curves in thermal analysis measurement for Examples 1 to 4 and Comparative Example 1 of the present invention.
  • 4 is a graph showing the relationship between the draw ratio at 50 to 250 ° C. and the average linear thermal expansion coefficient for Examples 1 to 4 and Comparative Examples 1 to 4 of the present invention.
  • 6 is a graph showing the relationship between the draw ratio and Young's modulus for Examples 1 to 4 and Comparative Examples 2 to 4 of the present invention.
  • 6 is a graph showing the relationship between the draw ratio and the breaking strength for Examples 1 to 4 and Comparative Examples 2 to 4 of the present invention.
  • the multi-branched polyimide material according to the present invention is obtained by polymerizing pyromellitic anhydride (hereinafter also referred to as PMDA) and 1,3,5-tris (4-aminophenoxy) benzene (hereinafter also referred to as TAPOB®).
  • PMDA pyromellitic anhydride
  • TAPOB® 1,3,5-tris (4-aminophenoxy) benzene
  • the multi-branched polyimide means a polyimide having a so-called tree-like structure having many terminals in one molecule and a molecular structure.
  • Multi-branched polyimide has a random three-dimensional structure, and its molecular structure is composed of many benzene rings and has a very rigid skeleton.
  • the multi-branched structure is substantially spherical, the degree of freedom of the molecular chain is low, and deformation does not easily occur.
  • the stretching process is performed, in the linear structure, the polymer chain is stretched and changed into a chain state and oriented, whereas in the multi-branched structure, the substantially spherical molecule changes into an elliptical shape as a whole. , Plane orientation.
  • the heat resistant film according to the present invention is a heat resistant film made of the above multi-branched polyimide material.
  • the method for producing a multibranched polyimide film according to the present invention comprises polymerizing pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene to form a film comprising a multibranched polyamic acid, This is a method for producing a multi-branched polyimide film in which a film comprising a branched polyamic acid is stretched so as to have a stretching ratio of 0.05 to 0.50 and imidized.
  • the multi-branched polyimide material heat-resistant film, ie, multi-branched polyimide film
  • heat-resistant film ie, multi-branched polyimide film
  • the synthesis of a multi-branched polyamic acid by polymerizing pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene is relatively low temperature, specifically 100 ° C. or less, preferably 50 ° C. It is preferable to carry out under the following temperature conditions.
  • the lower limit of the temperature condition for the synthesis of the multibranched polyamic acid is preferably equal to or higher than the melting point of the solvent to be used (solvent ⁇ described later). This is because if the temperature is lower than this, the solvent freezes and hinders synthesis.
  • the temperature for synthesizing the hyperbranched polyamic acid is preferably ⁇ 20 ° C. or higher.
  • the synthesis time was set so that the reaction between pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene proceeded sufficiently and the amount of both compounds used. It is determined appropriately according to
  • reaction of pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene is carried out by using 1,3,5-tris (4-amino) Phenoxy) benzene is preferably blended at a ratio of 0.3 to 1.2 molar equivalents. Furthermore, 1,3,5-tris (4-aminophenoxy) benzene is blended at a ratio of 0.4 to 1.1 molar equivalents when pyromellitic anhydride is 1 mole, More preferably.
  • solvent (with ⁇ ) examples include N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, tetramethylsulfone, hexamethylsulfone, hexamethylphosphoamide and the like.
  • aprotic polar solvents such as m-cresol, o-cresol, m-chlorophenol, o-chlorophenol and the like, or ether solvents such as dioxane, tetrahydrofuran and diglyme. .
  • ether solvents such as dioxane, tetrahydrofuran and diglyme.
  • solvents can be used alone or as a mixed solvent composed of two or more kinds.
  • the reaction of pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene using a solvent as described above is preferably performed in an inert gas atmosphere such as nitrogen gas or various rare gases. Implemented.
  • the synthesis of hyperbranched polyamic acid by polymerizing pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene is carried out according to the above-mentioned various conditions, for example, according to the following procedure.
  • a multi-branched polyamic acid solution can be obtained by gradually adding the TAPOB soot solution to the pyromellitic anhydride solution and stirring for a predetermined time.
  • the polymerization of pyromellitic anhydride and 1,3,5-tris (4-aminophenoxy) benzene should be carried out so as to obtain a multibranched polyamic acid having a styrene-equivalent number average molecular weight of 5000 to 100,000. It is more preferable to carry out so as to obtain a multibranched polyamic acid having a number average molecular weight in terms of styrene of 10,000 to 50,000.
  • the film-forming property is poor and it is difficult to create a film having sufficient strength, while the number average molecular weight of the multibranched polyamic acid is too large.
  • a gel is formed and a homogeneous film is not formed.
  • the multi-branched polyimide material of the present invention has an average linear thermal expansion coefficient at ⁇ 50 to 250 ° C. of ⁇ 1.0 to 28.0 ppm / ° C.
  • the multibranched polyimide is obtained.
  • the average linear thermal expansion coefficient at 50 to 250 ° C. is a thermomechanical analysis under the conditions of a tensile load of 50 mN, a heating rate of 5 ° C./min, and a nitrogen atmosphere (nitrogen inflow rate is 100 mL / min).
  • the temperature is once raised from room temperature (for example, 25 ° C.) to 350 ° C.
  • the dimensional change is obtained and this dimension is obtained.
  • the change is a value obtained by dividing the change by the temperature difference (200 ° C.) between the length of the test piece before tension at room temperature (for example, 25 ° C.) and the measured temperature (JIS-K-0129: 2005). JIS-K-7197: 1991).
  • a multi-branched polyimide having such a predetermined linear thermal expansion coefficient the following method is advantageously employed. That is, using a multi-branched polyamic acid solution prepared according to the above-described method, first, a multi-branched polyamic acid molded body having a shape that can be subjected to a stretching treatment (uniaxial stretching treatment) is produced, and then this multi-branched polyamic acid molded body is produced. By subjecting the branched polyamic acid molded body to stretching treatment (uniaxial stretching treatment) and imidization treatment, a multi-branched polyimide constituting the multi-branched polyimide material of the present invention is obtained.
  • a stretching treatment uniaxial stretching treatment
  • imidization treatment imidization treatment
  • a shape that can be subjected to stretching treatment various shapes such as a film shape, a plate shape, and a rod shape can be adopted depending on the use of the multi-branched polyimide material.
  • the shape is preferred.
  • the production of a multi-branched polyamic acid molded article having a shape that can be subjected to a stretching treatment is a technique according to the shape, and any technique can be used as long as it is conventionally known. It can be adopted.
  • a method for producing a film-like multibranched polyamic acid molded product multibranched polyamic acid film
  • a multibranched polyamide acid solution is thinly spread on a predetermined substrate and the solvent is removed to remove the multibranched polyamide.
  • a casting method for obtaining an acid film can be exemplified.
  • the thus obtained multi-branched polyamic acid molded article having a form capable of being subjected to a stretching treatment is subjected to a stretching treatment (uniaxial stretching treatment) and an imidization treatment.
  • the draw ratio in the drawing treatment is preferably 0.05 to 0.50 times, more preferably 0.10 to 0.50 times, and still more preferably 0.20 to 0.50 times. 0.50 times, particularly preferably 0.20 to 0.40 times. If the draw ratio is less than 0.05 times, the resulting multibranched polyimide may not be able to enjoy the effect of the drawing treatment (reduction in average linear thermal expansion coefficient) effectively, while 0.50 This is because if the stretching treatment exceeds twice, the elongation at break of the multi-branched polyamic acid molded article is exceeded, and the film may be broken.
  • the draw ratio in the present specification and claims means that calculated from the following formula.
  • any conventionally known technique can be adopted as long as it is a technique capable of uniaxial stretching, and it can be carried out using various uniaxial stretching apparatuses.
  • any imidation treatment can be employed as long as it is a conventionally known treatment method for imidizing polyamic acid.
  • heat treatment for example, 250 to 350 ° C. in a reducing atmosphere
  • reducing atmosphere for example, 250 to 350 ° C.
  • the order of performing the stretching treatment and the imidization treatment on the polyamic acid molded body is not particularly limited as long as the desired effects can be obtained by the respective treatments.
  • the imidization treatment is performed after the stretching treatment, but also the stretching treatment and the imidization treatment can proceed simultaneously.
  • the target multi-branched polyimide of the present invention can be obtained by subjecting the multi-branched polyamic acid molded article to stretching treatment and imidization treatment.
  • the thus obtained multi-branched polyimide has a relatively low average linear thermal expansion coefficient (CTE) of ⁇ 1.0 to 28.0 ppm / ° C. at 50 to 250 ° C., and the polyimide inherently has it. In addition to excellent mechanical properties, it also exhibits excellent dimensional stability at 50 to 250 ° C., which is higher than room temperature.
  • the average linear thermal expansion coefficient (CTE) of the multi-branched polyimide at 50 to 250 ° C.
  • the multi-branched polyimide material of the present invention comprising such a multi-branched polyimide is an interlayer insulating film or protective film of a semiconductor element, or a base film such as a flexible printed wiring board used for various electronic devices or solar cells, or the like. It can be advantageously used in applications such as coverlays.
  • the present invention is not limited to the above-described embodiment.
  • the multiple according to the present invention may be used as long as the object of the present invention is not impaired. Included in the category of branched polyimide materials.
  • the average linear thermal expansion coefficient (CTE), Young's modulus, breaking strength and breaking elongation were measured or calculated according to the following methods.
  • thermomechanical analyzer thermo / stress / strain measuring apparatus, model name: TMA / SS6100
  • SEIKO instruments thermomechanical analyzer
  • the measurement was performed at a measurement temperature of 50 to 250 ° C. under a tensile load of 50 mN, a temperature increase rate of 5 ° C./min, and a nitrogen atmosphere (nitrogen inflow rate was 100 mL / min).
  • the temperature is once raised from room temperature (for example, 25 ° C.) to 350 ° C.
  • the dimensional change is obtained and this dimension is obtained.
  • the change was divided by the length of the test piece before tension at room temperature (for example, 25 ° C.) and the temperature difference (200 ° C.) between the measured temperatures to determine the average linear thermal expansion coefficient (CTE).
  • test piece multi-branched polyimide film or linear polyimide film
  • a film prepared to a film thickness of 0.03 mm was appropriately stretched and then cut into a size of 30 mm ⁇ 3 mm. I did it. Therefore, the thickness of the test piece at the time of measuring the average linear thermal expansion coefficient is not necessarily the same (0.03 mm).
  • the Young's modulus (GPa) was calculated from the initial gradient of the obtained stress-strain curve, and the breaking strength (MPa) and breaking elongation (%) were determined from the strength and elongation length when the film broke.
  • the obtained DMAc solution of acid anhydride-terminated multi-branched polyamic acid was cast on a polyester film and dried at 85 ° C. for 1 hour to obtain a semi-dried multi-branched polyamic acid film.
  • the size of the multi-branched polyamic acid film is 80 mm ⁇ 80 mm ⁇ 0.03 mm.
  • Example 1 Both ends of the obtained semi-dried multi-branched polyamic acid film were fixed in parallel to a stretching jig, and 0.05 times for Example 1 was carried out based on the dimensions of the original film (length in the stretching direction).
  • the uniaxial stretching process was performed by widening the jig interval at both ends until the stretching ratio was 0.10 times for Example 2, 0.20 times for Example 3, and 0.40 times for Example 4. .
  • Each film after the uniaxial stretching treatment was subjected to a heat treatment in a nitrogen atmosphere at 100 ° C. for 1 hour, 200 ° C. for 1 hour, and further at 300 ° C. for 1 hour to obtain a multibranched polyimide film (Examples 1 to 4).
  • Table 1 shows measured values or calculation results of physical property values [average linear thermal expansion coefficient (CTE), Young's modulus, breaking strength, and breaking elongation] of each multi-branched polyimide film.
  • CTE average linear thermal expansion coefficient
  • Young's modulus Young's modul
  • Example 1 The multi-branched polyamic acid film obtained by the same method as in Examples 1 to 4 was subjected to heat treatment under the same conditions as in Examples 1 to 4 without performing uniaxial stretching (stretching ratio was 0.00). To give a multi-branched polyimide film.
  • the size of the multi-branched polyimide film is 80 mm ⁇ 80 mm ⁇ 0.03 mm.
  • Table 1 below shows measured values or calculation results of physical property values [average linear thermal expansion coefficient (CTE), Young's modulus, breaking strength, and breaking elongation] of this multi-branched polyimide film.
  • CTE average linear thermal expansion coefficient
  • Young's modulus Young's modulus
  • breaking strength breaking elongation
  • the obtained semi-dried linear polyamic acid film was fixed to a stretching jig, and 0.25 times for Comparative Example 3 and Comparative Example 4 based on the original film dimension (length in the stretching direction).
  • Uniaxial stretching was performed in the same manner as in Examples 1 to 4 at a stretching ratio of 0.50. In Comparative Example 2, the uniaxial stretching process was not performed (the stretching ratio was 0.00).
  • each film was heat-treated in a nitrogen atmosphere at 100 ° C. for 1 hour, 200 ° C. for 1 hour, and further at 300 ° C. for 1 hour to obtain linear polyimide films (Comparative Examples 2 to 4).
  • Table 1 shows measured values or calculation results of physical property values [average linear thermal expansion coefficient (CTE), Young's modulus, breaking strength, and breaking elongation] of each linear polyimide film.
  • CTE average linear thermal expansion coefficient
  • Young's modulus Young's modulus
  • breaking strength breaking elongation
  • FIG. 1 shows TMA curves [vertical amount change (%), horizontal axis temperature (° C.)] as a result of thermal analysis measurement of the test pieces of Examples 1 to 4 and Comparative Example 1.
  • FIG. 2 is a graph showing the relationship between the draw ratio (times) at 50 to 250 ° C. and the average linear thermal expansion coefficient (CTE) (ppm / ° C.) of Examples 1 to 4 and Comparative Examples 1 to 4.
  • CTE linear thermal expansion coefficient
  • the draw ratio is in the drawing direction (MD direction). A significant decrease in the average linear thermal expansion coefficient was observed as it increased.
  • the polyimide film (Examples 3 and 4) having a draw ratio of 0.2 to 0.4 times has a low average linear thermal expansion coefficient, and the average linear thermal expansion coefficient is less than 0 ppm / ° C. in a specific temperature range. The peculiar property of becoming was confirmed.
  • the multi-branched polyimide film having a draw ratio of 0.00 times of Comparative Example 1 has an average linear thermal expansion coefficient of 31.2 ppm / ° C., which is ⁇ 1.0 to 27. It can be confirmed that it is higher than 3 ppm / ° C.
  • the linear polyimide film of the comparative example 2, the comparative example 3, and the comparative example 4 showed the fall of an average linear thermal expansion coefficient as the draw ratio became large with respect to the extending
  • FIG. 3 is a graph showing the relationship between the draw ratio (times) and Young's modulus (GPa) of Examples 1 to 4 and Comparative Examples 2 to 4, and FIG. 4 is a graph of Examples 1 to 4 and Comparative Examples 2 to 4. The graphs of the relationship between the draw ratio (times) and the breaking strength (MPa) are respectively shown.
  • the multi-branched polyimide films (Examples 1 to 4) showed an increasing tendency with respect to the Young's modulus and the breaking strength in the stretching direction (MD direction) by the stretching treatment. It turns out that a polyimide film (Comparative Examples 1 and 2) is comparable.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention concerne une matière à base de polyimide multi-ramifié qui présente d'excellentes propriétés mécaniques ainsi qu'une excellente stabilité dimensionnelle, un film résistant à la chaleur et un procédé de production d'un film à base de polyimide multi-ramifié. Une matière à base de polyimide multi-ramifié qui a un coefficient de dilatation thermique linéaire moyen à 50 à 250°C de -1,0 à 28,0 ppm/°C est formé par polymérisation d'anhydride pyromellitique (PMDA) et de 1,3,5-tris(4-aminophénoxy)benzène (TAPOB).
PCT/JP2011/070330 2010-09-07 2011-09-07 Matière à base de polyimide multi-ramifié, film résistant à la chaleur et procédé de production d'un film à base de polyimide multi-ramifié Ceased WO2012033115A1 (fr)

Applications Claiming Priority (2)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006025327A1 (fr) * 2004-08-30 2006-03-09 National University Corporation Nagoya Institute Of Technology Matière hybride de polyimide multibranche
JP2006131706A (ja) * 2004-11-04 2006-05-25 Nagoya Institute Of Technology ポリイミド系低誘電材料および高効率分離膜
JP2007246772A (ja) * 2006-03-17 2007-09-27 Nagoya Industrial Science Research Inst 多分岐ポリイミド系ハイブリッド材料
WO2008114798A1 (fr) * 2007-03-19 2008-09-25 Ibiden Co., Ltd. Polyimide poreux
JP2008231170A (ja) * 2007-03-19 2008-10-02 Nagoya Industrial Science Research Inst 感光性多分岐ポリイミド系ハイブリッド前駆体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006025327A1 (fr) * 2004-08-30 2006-03-09 National University Corporation Nagoya Institute Of Technology Matière hybride de polyimide multibranche
JP2006131706A (ja) * 2004-11-04 2006-05-25 Nagoya Institute Of Technology ポリイミド系低誘電材料および高効率分離膜
JP2007246772A (ja) * 2006-03-17 2007-09-27 Nagoya Industrial Science Research Inst 多分岐ポリイミド系ハイブリッド材料
WO2008114798A1 (fr) * 2007-03-19 2008-09-25 Ibiden Co., Ltd. Polyimide poreux
JP2008231170A (ja) * 2007-03-19 2008-10-02 Nagoya Industrial Science Research Inst 感光性多分岐ポリイミド系ハイブリッド前駆体

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