WO2016056595A1 - Polyimide precursor composition and method for producing insulating coating layer using same - Google Patents

Polyimide precursor composition and method for producing insulating coating layer using same Download PDF

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Publication number
WO2016056595A1
WO2016056595A1 PCT/JP2015/078502 JP2015078502W WO2016056595A1 WO 2016056595 A1 WO2016056595 A1 WO 2016056595A1 JP 2015078502 W JP2015078502 W JP 2015078502W WO 2016056595 A1 WO2016056595 A1 WO 2016056595A1
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mol
precursor composition
coating layer
polyimide precursor
polyimide
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PCT/JP2015/078502
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French (fr)
Japanese (ja)
Inventor
武史 寺田
剛成 中山
圭吾 長尾
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宇部興産株式会社
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Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Priority to JP2016553136A priority Critical patent/JP7242157B2/en
Publication of WO2016056595A1 publication Critical patent/WO2016056595A1/en
Priority to JP2022212592A priority patent/JP2023033360A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes

Definitions

  • the present invention relates to a polyimide precursor composition capable of efficiently producing a polyimide insulating coating layer having excellent heat resistance and mechanical properties, and a method for producing an insulating coating layer using the same.
  • Polyimide resin is known as a resin excellent in heat resistance and is widely used in various fields. For example, in addition to high heat resistance, it has a low dielectric constant and excellent mechanical properties, so it is used as an insulating layer for electric wires with high required properties.
  • Patent Document 1 discloses an insulating layer characterized in that an insulating layer obtained by imidizing polyamic acid obtained by reaction of biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether is provided on a core wire. A covered electric wire is described, and it is described that this polyimide insulating covered electric wire has excellent resistance to thermal deterioration.
  • the polyimide may become crystalline depending on the combination of the tetracarboxylic acid component and the diamine component, and as a result, the conditions for imidizing the polyamic acid that is the polyimide precursor may be limited.
  • the conditions for imidizing the polyamic acid that is the polyimide precursor may be limited.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used as the tetracarboxylic acid component, a crystalline polyimide resin can be easily obtained, and depending on imidization conditions, particularly rapid If imidization is attempted by a short heat treatment by increasing the temperature, partial crystallization is likely to occur.
  • productivity is increased by increasing the temperature rise rate. In some cases, it could not be increased.
  • Patent Document 2 describes a method that can form a polyimide insulating coating layer without causing crystallization even if the step is performed. Specifically, it is a method for producing a polyimide insulating coating layer including a step of applying and baking a polyimide precursor composition to a substrate, wherein the polyimide precursor composition is 3,3 ′, 4 as a tetracarboxylic acid component.
  • the present invention provides a method capable of forming a polyimide insulating coating layer without defects even when rapid heating is performed when imidizing polyamic acid to form a polyimide insulating coating layer. That is, the present invention provides a polyimide precursor composition capable of forming a polyimide resin insulating coating layer excellent in heat resistance and mechanical properties in a short time without causing crystallization, and also provides the polyimide precursor.
  • a polyimide precursor composition capable of forming a polyimide resin insulating coating layer excellent in heat resistance and mechanical properties in a short time without causing crystallization
  • an industrially advantageous method for producing an insulating coating layer in which a polyimide resin insulating coating layer having excellent heat resistance and mechanical properties is formed in a short time without causing crystallization using the body composition. For the purpose.
  • a polyimide precursor composition comprising a polyamic acid and a solvent,
  • the polyamic acid comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or any one of 50 to 100
  • a polyimide precursor composition for forming a polyimide insulating coating layer which is capable of producing a polyimide film larger than (m 2 ⁇ 24h).
  • the tetracarboxylic acid component includes 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, and the diamine component includes paraphenylenediamine and 4,4′-diaminodiphenyl ether, or any one of them.
  • the tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component is paraphenylenediamine, 4,4′-diaminodiphenyl ether and 2,2 It consists of one or more diamines selected from the group consisting of '-bis [4- (4-aminophenoxy) phenyl] propane, and 30% 2,2'-bis [4- (4-aminophenoxy) phenyl] propane.
  • Item 2 The polyimide precursor composition for forming a polyimide insulating coating layer according to Item 1, which comprises ⁇ 100 mol%. 4).
  • the tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component contains 4,4′-diaminodiphenyl ether and 4,4′-methylenebis ( 2.
  • the polyimide insulation according to item 1, comprising at least one diamine selected from the group consisting of 2,6-xylysine) and containing 20 to 100 mol% of 4,4′-methylenebis (2,6-xylidine).
  • a polyimide precursor composition for forming a coating layer comprising at least one diamine selected from the group consisting of 2,6-xylysine) and containing 20 to 100 mol% of 4,4′-methylenebis (2,6-xylidine).
  • a method for producing a polyimide insulating coating layer comprising a step of applying and baking a polyimide precursor composition on a substrate,
  • the polyimide precursor composition contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or 50 of them.
  • a water vapor transmission coefficient is obtained by heat treatment under the condition that the polyamic acid is obtained from a tetracarboxylic acid component and a diamine component contained in an amount of ⁇ 100 mol% and the maximum heating temperature is 300 to 500 ° C.
  • the time for heating the polyimide precursor composition is 10 to 180 seconds,
  • the average rate of temperature increase from 100 ° C. to 280 ° C. is 5 ° C./s or more,
  • the tetracarboxylic acid component includes 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride
  • the diamine component includes paraphenylenediamine and 4,4′-diaminodiphenyl ether, or any one of them. Item 6.
  • the tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component is paraphenylenediamine, 4,4′-diaminodiphenyl ether and 2,2 It consists of one or more diamines selected from the group consisting of '-bis [4- (4-aminophenoxy) phenyl] propane, and 30% 2,2'-bis [4- (4-aminophenoxy) phenyl] propane.
  • the tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component contains 4,4′-diaminodiphenyl ether and 4,4′-methylenebis (
  • the insulation coating according to Item 5, comprising at least one diamine selected from the group consisting of 2,6-xylysine) and containing 20 to 100 mol% of 4,4′-methylenebis (2,6-xylidine) Layer manufacturing method.
  • a polyimide precursor composition capable of forming a polyimide resin insulating coating layer having excellent heat resistance and mechanical properties in a short time without causing crystallization. That is, by using the polyimide precursor composition of the present invention, a polyimide resin insulating coating layer having excellent heat resistance and mechanical properties can be formed in a short time without causing crystallization.
  • the polyimide precursor composition of the present invention and the method for producing an insulating coating layer of the present invention using the polyimide precursor composition can be suitably applied particularly to the production of insulated wires, have excellent heat resistance, and have defects in the insulating coating layer. This makes it possible to efficiently manufacture a highly reliable insulated wire that does not have any.
  • the polyimide precursor composition of the present invention has 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic acid dihydrate as a tetracarboxylic acid component.
  • An anhydride is used and is characterized by containing a polyamic acid that gives a polyimide film having a specific water vapor transmission coefficient.
  • the polyamic acid used in the present invention contains a tetracarboxylic acid component (the tetracarboxylic acid component includes a tetracarboxylic dianhydride) and a diamine component in a solvent, for example, water or an organic solvent, or water. It can be obtained by reacting in a mixed solvent of organic solvents.
  • a solvent for example, water or an organic solvent, or water. It can be obtained by reacting in a mixed solvent of organic solvents.
  • This polyamic acid is obtained from a tetracarboxylic acid component containing 50 to 100 mol% of biphenyltetracarboxylic dianhydride and a diamine component.
  • Biphenyltetracarboxylic dianhydride is a generic term including a plurality of isomers, and includes 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydrides and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydrides are included therein.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is contained in an amount of 50 to 100 mol%.
  • a polyamic acid obtained from a tetracarboxylic acid component and a diamine component is used.
  • the polyamic acid used in the present invention is obtained by subjecting a polyimide film having a water vapor transmission coefficient larger than 1.7 g ⁇ mm / (m 2 ⁇ 24 h) by heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C. It can be manufactured.
  • the tetracarboxylic acid component used in the present invention is mainly composed of 50 to 100 mol%, more preferably 70 to 100 mol%, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2 , 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or one of them.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is preferably used as a main component from the viewpoint of heat resistance and mechanical properties.
  • 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride may be used in an amount of 50 mol% or less, or a tetracarboxylic acid component other than biphenyltetracarboxylic dianhydride (tetra Carboxylic dianhydride) may be used in the range of 50 mol% or less.
  • tetracarboxylic dianhydride that can be used in combination with biphenyltetracarboxylic dianhydride in the present invention is not particularly limited, but aromatic tetracarboxylic dianhydrides and alicyclic rings are obtained from the properties of the resulting polyimide.
  • tetracarboxylic dianhydride is preferred.
  • Anhydrous, m-terphenyltetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc. are preferred Can be mentioned.
  • tetracarboxylic acid component other than biphenyltetracarboxylic dianhydride it is particularly preferable to use 4,4′-oxydiphthalic dianhydride or pyromellitic dianhydride because of the characteristics of the resulting polyimide.
  • the tetracarboxylic dianhydride described above need not be one kind, and may be a mixture of plural kinds.
  • the diamine that can be used in the present invention is not particularly limited. 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine , Benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylpropane, 2,4-diaminotoluene, bis (4-amino- 3-carboxyphenyl) methane, 1,3-bis (4-amino) Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl]
  • the polyamic acid used in the present invention can produce a polyimide film having a water vapor transmission coefficient larger than 1.7 g ⁇ mm / (m 2 ⁇ 24 h) by heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C. is required.
  • a polyimide film having a water vapor transmission coefficient of 1.8 g ⁇ mm / (m 2 ⁇ 24 h) or more can be produced.
  • the water vapor permeability coefficient of the resulting polyimide film is smaller than this, partial crystallization is likely to occur if imidization is attempted by a short heat treatment with rapid temperature increase in the production of a polyimide insulating coating layer. .
  • the polyamic acid used in the polyimide precursor composition of the present invention provides a polyimide resin that is easily permeable to gas, the solvent is likely to evaporate, and the problem of crystallization under conditions where the rate of temperature increase is high is less likely to occur.
  • polyamic acid having a water vapor transmission coefficient larger than 1.7 g ⁇ mm / (m 2 ⁇ 24 h) of the polyimide film obtained by heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C. include, for example, tetracarboxylic acid
  • the acid component include polyamic acid containing 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride.
  • the diamine component preferably contains 50 to 100 mol% of paraphenylenediamine and 4,4′-diaminodiphenyl ether, or any one of them.
  • the polyamic acid contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, and paraphenylenediamine, 4,4 ′ as a diamine component.
  • the polyamic acid includes 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, 4,4′-diaminodiphenyl ether as a diamine component, and Polyamic acid comprising one or more diamines selected from the group consisting of 4,4′-methylenebis (2,6-xylidine) and containing 20 to 100 mol% of 4,4′-methylenebis (2,6-xylidine) Is mentioned.
  • the polyamic acid used in the present invention reacts with an approximately equimolar amount of tetracarboxylic dianhydride and diamine in a solvent at a relatively low temperature of 100 ° C. or lower, preferably 80 ° C. or lower in order to suppress the imidization reaction. By making it, it can be obtained as a polyamic acid solution.
  • the reaction temperature is usually 25 ° C. to 100 ° C., preferably 40 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C.
  • the reaction time is about 0.1 to 24 hours, preferably About 2 to 12 hours.
  • the reaction can be carried out in an air atmosphere, but is usually suitably carried out in an inert gas, preferably a nitrogen gas atmosphere.
  • the approximately equimolar tetracarboxylic dianhydride and diamine are specifically about 0.90 to 1.10, preferably 0.95 to about their molar ratio [tetracarboxylic dianhydride / diamine]. It is about 1.05.
  • the solvent used in the present invention may be any solvent as long as it can polymerize polyamic acid, and may be an aqueous solvent or an organic solvent.
  • the solvent may be a mixture of two or more, and a mixed solvent of two or more organic solvents or a mixed solvent of water and one or more organic solvents can also be suitably used.
  • the organic solvent that can be used in the present invention is not particularly limited.
  • the solvent used for this reaction can be a solvent contained in the polyimide precursor composition of the present invention.
  • the polyamic acid used in the present invention is not limited, but the logarithmic viscosity measured at a temperature of 30 ° C. and a concentration of 0.5 g / 100 mL is 0.2 or more, preferably 0.4 or more, particularly preferably 0.6 or more. Is preferred. When the logarithmic viscosity is lower than the above range, it may be difficult to obtain a polyimide having high characteristics because the molecular weight of the polyamic acid is low.
  • the polyimide precursor composition used in the present invention is not limited in the solid content concentration due to the polyamic acid, but is preferably 5% by mass to 45% by mass, more preferably based on the total amount of the polyamic acid and the solvent.
  • the content is preferably 5% by mass to 40% by mass, more preferably more than 5% by mass and 30% by mass.
  • the solution viscosity at 30 ° C. of the polyimide precursor composition used in the present invention is not limited, but is preferably 1000 Pa ⁇ sec or less, more preferably 0.5 to 500 Pa ⁇ sec, still more preferably 1 to 300 Pa ⁇ sec, Particularly preferably, the pressure is 2 to 200 Pa ⁇ sec.
  • the polyimide precursor composition is converted into polyimide by removing the solvent by heat treatment and imidizing (dehydrating ring closure).
  • a polyimide insulating coating layer is obtained. Therefore, it is possible to employ a process of raising the temperature in a short time and baking at a high temperature.
  • the time for heating the polyimide precursor composition is 10 to 180 seconds, and the average temperature increase rate from 100 ° C. to 280 ° C. In this process, the temperature is raised under the condition of 5 ° C./s or more, and the maximum heating temperature is 300 to 500 ° C.
  • the polyimide precursor composition as described above is applied to a substrate by a known method, and heated (baked) to form a polyimide insulating coating layer.
  • the time for heating the polyimide precursor composition is 10 to 180 seconds, and the average temperature increase rate from 100 ° C. to 280 ° C. is 5
  • the maximum heating temperature can be 300 to 500 ° C.
  • the upper limit of the average rate of temperature increase from 100 ° C. to 280 ° C. is not particularly limited, but for example, 50 ° C./s or less is preferable.
  • the average rate of temperature increase from 100 ° C. to 300 ° C. may be 5 ° C./s or more (ie, from 100 ° C. to 300 ° C. within 40 seconds).
  • the average rate of temperature increase up to 500 ° C. may be 5 ° C./s or more.
  • the average rate of temperature increase up to 100 ° C. is not particularly limited, but may be 5 ° C./s or more.
  • the temperature is increased from room temperature to the maximum heating temperature.
  • the temperature may be raised at a constant rate of temperature rise, the rate of temperature rise may be changed during the heat treatment, and the temperature may be raised stepwise.
  • the heat treatment for imidization can be performed, for example, in an air atmosphere or an inert gas atmosphere.
  • polyimide insulating coating layer can also be formed by heat-treating the polyimide precursor composition of the present invention under conditions other than those described above.
  • a base material is not specifically limited, According to a use, it selects suitably.
  • the thickness of the polyimide insulating coating layer to be formed is not particularly limited, and is appropriately selected according to the application.
  • the polyimide insulating coating layer obtained by the present invention is an insulating member (coating layer) having high voltage resistance, heat resistance, and moist heat resistance. Therefore, it can be particularly suitably used in the fields of electric / electronic parts, the automobile field, the aerospace field, etc., and can also be used in the fields of coils for HV car motors and micro motors.
  • Solid content concentration [% by mass] (w 2 / w 1 ) ⁇ 100 ⁇ Solution viscosity (rotational viscosity)> It measured at 30 degreeC using the Tokimec E-type viscosity meter.
  • the prepared polyimide precursor composition is coated on a glass substrate, heated in a hot air oven at 80 ° C. for 30 minutes, and then cured by heating at 350 ° C. for 30 minutes to form a polyimide film having a thickness of about 25 ⁇ m. Produced. The obtained polyimide film was cut into a width of 10 mm and a length of 100 mm to obtain a test piece.
  • Example 1 To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 396 g of NMP was added as a solvent, and 40.05 g (0.2 mol) of ODA was added thereto. Stir for hours to dissolve. To this solution, 58.84 g (0.2 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.5% by mass and a solution viscosity of 5.0 Pa ⁇ s. Got.
  • This polyimide precursor composition was coated on a polyimide film having a thickness of 50 ⁇ m.
  • the obtained sample was placed on a SUS plate previously heated to 380 ° C. and held for 1 minute to form an insulating coating layer having a thickness of approximately 25 ⁇ m.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • Example 2 To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 396 g of NMP was added as a solvent, and 40.05 g (0.2 mol) of ODA was added thereto. Stir for hours to dissolve. To this solution, 47.08 g (0.16 mol) of s-BPDA and 11.77 g (0.04 mol) of a-BPDA were added and stirred at 50 ° C. for 3 hours to obtain a solid concentration of 18.5% by mass. A polyimide precursor composition having a solution viscosity of 5.0 Pa ⁇ s was obtained.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • Example 3 386 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.95 g (0.24 mol) of PPD was added thereto. Stir for hours to dissolve. 70.61 g (0.24 mol) of a-BPDA was added to this solution, and the mixture was stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.2% by mass and a solution viscosity of 5.0 Pa ⁇ s. Got.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • Example 4 386 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.95 g (0.24 mol) of PPD was added thereto. Stir for hours to dissolve. To this solution, 35.31 g (0.12 mol) of s-BPDA and 35.31 g (0.12 mol) of a-BPDA were added and stirred at 50 ° C. for 3 hours to obtain a solid concentration of 18.2% by mass. A polyimide precursor composition having a solution viscosity of 5.0 Pa ⁇ s was obtained.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 1.
  • Example 5 To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 395 g of NMP was added as a solvent, and 57.47 g (0.14 mol) of BAPP was added thereto. Stir for hours to dissolve. To this solution, 41.19 g (0.14 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 19.0% by mass and a solution viscosity of 5.0 Pa ⁇ s. Got.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • Example 6 401 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, to which 22.17 g (0.05 mol) of BAPP and 25.23 g of ODA ( 0.13 mol) was added and stirred at 50 ° C. for 1 hour to dissolve.
  • 22.17 g (0.05 mol) of BAPP and 25.23 g of ODA ( 0.13 mol) was added and stirred at 50 ° C. for 1 hour to dissolve.
  • 52.96 g (0.18 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.7% by mass and a solution viscosity of 5.0 Pa ⁇ s. Got.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • Example 7 To a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, 393 g of NMP was added as a solvent, and 45.98 g (0.11 mol) of BAPP and 5.19 g of PPD ( 0.05 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. 47.08 g (0.16 mol) of s-BPDA was added to this solution and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.8% by mass and a solution viscosity of 5.0 Pa ⁇ s. Got.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • Example 8 To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 404 g of NMP was added as a solvent, and 10.18 g (0.04 mol) of MDX and 32.04 g of ODA ( 0.16 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 58.84 g (0.2 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.6% by mass and a solution viscosity of 5.0 Pa ⁇ s. Got.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.
  • An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition.
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • the results of state observation and property evaluation are shown in Table 2.

Abstract

The present invention pertains to a polyimide precursor composition for forming a polyimide insulating coating layer, the composition characterized by enabling production of a polyimide film that comprises a solvent and a polyamic acid obtained from a diamine component and a tetracarboxylic acid component containing 50 to 100 mol% of 3,3',4,4'-biphenyl tetracarboxylic dianhydride and/or 2,3,3',4'-biphenyl tetracarboxylic dianhydride, and the polyimide film has a steam permeation coefficient greater than 1.7 g·mm/(m2·24H) as a result of carrying out a heat treatment of the polyamic acid under conditions where the maximum heating temperature is 300 to 500˚C.

Description

ポリイミド前駆体組成物、およびそれを用いた絶縁被覆層の製造方法Polyimide precursor composition and method for producing insulating coating layer using the same
　本発明は、優れた耐熱性、機械的特性を有するポリイミド絶縁被覆層を効率よく製造することができるポリイミド前駆体組成物、およびそれを用いた絶縁被覆層の製造方法に関する。 The present invention relates to a polyimide precursor composition capable of efficiently producing a polyimide insulating coating layer having excellent heat resistance and mechanical properties, and a method for producing an insulating coating layer using the same.
　ポリイミド樹脂は、非常に耐熱性に優れた樹脂として知られており、様々な分野で広く利用されている。例えば、高い耐熱性に加えて、低誘電率で機械特性にも優れるため、要求特性の高い電線の絶縁層として用いられている。特許文献１には、芯線上に、ビフェニルテトラカルボン酸二無水物と４、４’－ジアミノジフェニルエーテルとの反応により得られるポリアミック酸をイミド化した絶縁層が設けられていることを特徴とする絶縁被覆電線が記載されており、このポリイミド絶縁被覆電線は、熱劣化に対する優れた抵抗性を有していることが記載されている。 Polyimide resin is known as a resin excellent in heat resistance and is widely used in various fields. For example, in addition to high heat resistance, it has a low dielectric constant and excellent mechanical properties, so it is used as an insulating layer for electric wires with high required properties. Patent Document 1 discloses an insulating layer characterized in that an insulating layer obtained by imidizing polyamic acid obtained by reaction of biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether is provided on a core wire. A covered electric wire is described, and it is described that this polyimide insulating covered electric wire has excellent resistance to thermal deterioration.
　ポリイミドは、テトラカルボン酸成分とジアミン成分の組み合わせによって結晶性となることがあり、その結果、ポリイミド前駆体であるポリアミック酸をイミド化する際の条件に制限が生じることがある。例えば、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いると、結晶性のポリイミド樹脂が得られ易く、イミド化の条件によっては、特に、急速な昇温による短時間の熱処理によりイミド化を行おうとすると、部分的な結晶化を起こし易い。そのため、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸をイミド化してポリイミド層を形成する場合、昇温速度を上げて生産性を高めることができない場合があった。 The polyimide may become crystalline depending on the combination of the tetracarboxylic acid component and the diamine component, and as a result, the conditions for imidizing the polyamic acid that is the polyimide precursor may be limited. For example, when 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used as the tetracarboxylic acid component, a crystalline polyimide resin can be easily obtained, and depending on imidization conditions, particularly rapid If imidization is attempted by a short heat treatment by increasing the temperature, partial crystallization is likely to occur. Therefore, when a polyimide layer is formed by imidizing polyamic acid using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, productivity is increased by increasing the temperature rise rate. In some cases, it could not be increased.
　このようなテトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸をイミド化してポリイミド絶縁被覆層を形成する方法であって、急速な昇温を行っても、結晶化を起こすことなく、ポリイミド絶縁被覆層を形成できる方法が特許文献２に記載されている。具体的には、基材にポリイミド前駆体組成物を塗布、焼付けする工程を有するポリイミド絶縁被覆層の製造方法であって、ポリイミド前駆体組成物が、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸と、イミダゾール類及びアミン化合物からなる群より選択される塩基性化合物とを含み、かつ、焼付け工程において、ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上であり、最高加熱温度が３００～５００℃であることを特徴とする絶縁被覆層の製造方法が特許文献２に記載されている。 A method of forming a polyimide insulating coating layer by imidizing polyamic acid using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, Patent Document 2 describes a method that can form a polyimide insulating coating layer without causing crystallization even if the step is performed. Specifically, it is a method for producing a polyimide insulating coating layer including a step of applying and baking a polyimide precursor composition to a substrate, wherein the polyimide precursor composition is 3,3 ′, 4 as a tetracarboxylic acid component. , 4'-biphenyltetracarboxylic dianhydride and a basic compound selected from the group consisting of imidazoles and amine compounds, and heating the polyimide precursor composition in the baking step For 10 to 180 seconds, an average rate of temperature increase from 100 ° C. to 280 ° C. is 5 ° C./s or more, and a maximum heating temperature is 300 to 500 ° C. A method is described in Patent Document 2.
特開昭６１－２７３８０６号公報JP-A-61-273806 国際公開第２０１４／１４２１７３号パンフレットInternational Publication No. 2014/142173 Pamphlet
　本発明は、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および／または２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸をイミド化してポリイミド絶縁被覆層を形成する際に、急速な昇温を行っても欠陥なくポリイミド絶縁被覆層を形成できる方法を提供することを目的とする。すなわち、本発明は、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成できるポリイミド前駆体組成物を提供すること、また、このポリイミド前駆体組成物を用いて、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成する工業的に有利な絶縁被覆層の製造方法を提供することを目的とする。 In the present invention, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is used as the tetracarboxylic acid component. It is an object of the present invention to provide a method capable of forming a polyimide insulating coating layer without defects even when rapid heating is performed when imidizing polyamic acid to form a polyimide insulating coating layer. That is, the present invention provides a polyimide precursor composition capable of forming a polyimide resin insulating coating layer excellent in heat resistance and mechanical properties in a short time without causing crystallization, and also provides the polyimide precursor. Provided is an industrially advantageous method for producing an insulating coating layer in which a polyimide resin insulating coating layer having excellent heat resistance and mechanical properties is formed in a short time without causing crystallization using the body composition. For the purpose.
　本発明は以下の項に関する。
１．　ポリアミック酸と溶媒とを含むポリイミド前駆体組成物であって、
　前記ポリアミック酸が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸であり、かつ、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものであることを特徴とする、ポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。
２．　テトラカルボン酸成分が、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含み、ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、前記項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。
３．　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、前記項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。
４．　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、前記項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。 The present invention relates to the following items.
1. A polyimide precursor composition comprising a polyamic acid and a solvent,
The polyamic acid comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or any one of 50 to 100 A polyamic acid obtained from a tetracarboxylic acid component and a diamine component contained in a mol%, and when subjected to heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C., the water vapor transmission coefficient is 1.7 g · mm / A polyimide precursor composition for forming a polyimide insulating coating layer, which is capable of producing a polyimide film larger than (m 2 · 24h).
2. The tetracarboxylic acid component includes 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, and the diamine component includes paraphenylenediamine and 4,4′-diaminodiphenyl ether, or any one of them. Item 2. The polyimide precursor composition for forming a polyimide insulating coating layer according to Item 1, which comprises ˜100 mol%.
3. The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component is paraphenylenediamine, 4,4′-diaminodiphenyl ether and 2,2 It consists of one or more diamines selected from the group consisting of '-bis [4- (4-aminophenoxy) phenyl] propane, and 30% 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. Item 2. The polyimide precursor composition for forming a polyimide insulating coating layer according to Item 1, which comprises ˜100 mol%.
4). The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component contains 4,4′-diaminodiphenyl ether and 4,4′-methylenebis ( 2. The polyimide insulation according to item 1, comprising at least one diamine selected from the group consisting of 2,6-xylysine) and containing 20 to 100 mol% of 4,4′-methylenebis (2,6-xylidine). A polyimide precursor composition for forming a coating layer.
５．　基材にポリイミド前駆体組成物を塗布、焼付けする工程を有するポリイミド絶縁被覆層の製造方法であって、
　ポリイミド前駆体組成物が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸を含み、かつ、このポリアミック酸が、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものであり、
　焼付け工程において、
ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、
１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上であり、
最高加熱温度が３００～５００℃であることを特徴とする絶縁被覆層の製造方法。
６．　テトラカルボン酸成分が、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含み、ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、前記項５に記載の絶縁被覆層の製造方法。
７．　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、前記項５に記載の絶縁被覆層の製造方法。
８．　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、前記項５に記載の絶縁被覆層の製造方法。 5. A method for producing a polyimide insulating coating layer comprising a step of applying and baking a polyimide precursor composition on a substrate,
The polyimide precursor composition contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or 50 of them. A water vapor transmission coefficient is obtained by heat treatment under the condition that the polyamic acid is obtained from a tetracarboxylic acid component and a diamine component contained in an amount of ˜100 mol% and the maximum heating temperature is 300 to 500 ° C. Is capable of producing a polyimide film of greater than 1.7 g · mm / (m 2 · 24 h),
In the baking process,
The time for heating the polyimide precursor composition is 10 to 180 seconds,
The average rate of temperature increase from 100 ° C. to 280 ° C. is 5 ° C./s or more,
A method for producing an insulating coating layer, wherein the maximum heating temperature is 300 to 500 ° C.
6). The tetracarboxylic acid component includes 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, and the diamine component includes paraphenylenediamine and 4,4′-diaminodiphenyl ether, or any one of them. Item 6. The method for producing an insulating coating layer according to Item 5, which comprises ˜100 mol%.
7). The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component is paraphenylenediamine, 4,4′-diaminodiphenyl ether and 2,2 It consists of one or more diamines selected from the group consisting of '-bis [4- (4-aminophenoxy) phenyl] propane, and 30% 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. Item 6. The method for producing an insulating coating layer according to Item 5, which comprises ˜100 mol%.
8). The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the diamine component contains 4,4′-diaminodiphenyl ether and 4,4′-methylenebis ( The insulation coating according to Item 5, comprising at least one diamine selected from the group consisting of 2,6-xylysine) and containing 20 to 100 mol% of 4,4′-methylenebis (2,6-xylidine) Layer manufacturing method.
　本発明により、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成できるポリイミド前駆体組成物を提供することができる。すなわち、本発明のポリイミド前駆体組成物を用いることにより、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成することができる。本発明のポリイミド前駆体組成物、およびそれを用いた本発明の絶縁被覆層の製造方法は、特に、絶縁電線の製造に好適に適用でき、優れた耐熱性を有するとともに、絶縁被覆層に欠陥がない、信頼性の高い絶縁電線を効率よく製造することができる。 According to the present invention, it is possible to provide a polyimide precursor composition capable of forming a polyimide resin insulating coating layer having excellent heat resistance and mechanical properties in a short time without causing crystallization. That is, by using the polyimide precursor composition of the present invention, a polyimide resin insulating coating layer having excellent heat resistance and mechanical properties can be formed in a short time without causing crystallization. The polyimide precursor composition of the present invention and the method for producing an insulating coating layer of the present invention using the polyimide precursor composition can be suitably applied particularly to the production of insulated wires, have excellent heat resistance, and have defects in the insulating coating layer. This makes it possible to efficiently manufacture a highly reliable insulated wire that does not have any.
　本発明のポリイミド前駆体組成物は、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および／または２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を用いたものであり、特定の水蒸気透過係数を有するポリイミドフィルムを与えるポリアミック酸を含むことを特徴とする。 The polyimide precursor composition of the present invention has 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic acid dihydrate as a tetracarboxylic acid component. An anhydride is used and is characterized by containing a polyamic acid that gives a polyimide film having a specific water vapor transmission coefficient.
　本発明で用いるポリアミック酸は、テトラカルボン酸成分（テトラカルボン酸成分にはテトラカルボン酸二無水物も含まれる）とジアミン成分とを溶媒中で、例えば、水又は有機溶媒中で、又は水と有機溶媒の混合溶媒中で反応させることにより得られる。 The polyamic acid used in the present invention contains a tetracarboxylic acid component (the tetracarboxylic acid component includes a tetracarboxylic dianhydride) and a diamine component in a solvent, for example, water or an organic solvent, or water. It can be obtained by reacting in a mixed solvent of organic solvents.
　このポリアミック酸は、ビフェニルテトラカルボン酸二無水物を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるものである。ビフェニルテトラカルボン酸二無水物とは複数の異性体を含む総称であり、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、および２，２’，３，３’－ビフェニルテトラカルボン酸二無水物がこの中に含まれる。本発明においては、特に、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および／または２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸を用いる。 This polyamic acid is obtained from a tetracarboxylic acid component containing 50 to 100 mol% of biphenyltetracarboxylic dianhydride and a diamine component. Biphenyltetracarboxylic dianhydride is a generic term including a plurality of isomers, and includes 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydrides and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydrides are included therein. In the present invention, in particular, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is contained in an amount of 50 to 100 mol%. A polyamic acid obtained from a tetracarboxylic acid component and a diamine component is used.
　また、本発明で用いるポリアミック酸は、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造することができるものである。 Further, the polyamic acid used in the present invention is obtained by subjecting a polyimide film having a water vapor transmission coefficient larger than 1.7 g · mm / (m 2 · 24 h) by heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C. It can be manufactured.
　本発明で用いるテトラカルボン酸成分は、主成分が、すなわち５０～１００モル％、より好ましくは７０～１００モル％が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方である。特に、耐熱性や機械的特性の観点から、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を主成分として用いるのが好ましい。前述のとおり、通常、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いる場合、急速な昇温による短時間の熱処理によりイミド化を行おうとすると、部分的な結晶化を起こし易いが、本発明によれば、すなわち、そのポリアミック酸が、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものである場合、急速な昇温を行っても、結晶化を起こすことなく、ポリイミド層を形成できる。 The tetracarboxylic acid component used in the present invention is mainly composed of 50 to 100 mol%, more preferably 70 to 100 mol%, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2 , 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or one of them. In particular, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is preferably used as a main component from the viewpoint of heat resistance and mechanical properties. As described above, when 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is usually used as the tetracarboxylic acid component, imidization is attempted by a short heat treatment by rapid temperature increase. Although partial crystallization is likely to occur, according to the present invention, that is, when the polyamic acid can produce a polyimide film having a water vapor transmission coefficient larger than 1.7 g · mm / (m 2 · 24 h). Even if the temperature is increased rapidly, the polyimide layer can be formed without causing crystallization.
　本発明では、２，２’，３，３’－ビフェニルテトラカルボン酸二無水物を５０モル％以下の範囲で用いてもよいし、ビフェニルテトラカルボン酸二無水物以外のテトラカルボン酸成分（テトラカルボン酸二無水物）を５０モル％以下の範囲で用いてもよい。本発明でビフェニルテトラカルボン酸二無水物と組み合わせて用いることができるテトラカルボン酸二無水物は、特に限定するものではないが、得られるポリイミドの特性から芳香族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物が好ましい。例えば、ピロメリット酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、オキシジフタル酸二無水物、ジフェニルスルホンテトラカルボン酸二無水物、ｐ－ターフェニルテトラカルボン酸二無水物、ｍ－ターフェニルテトラカルボン酸二無水物、シクロブタン－１，２，３，４－テトラカルボン酸二無水物、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物などを好適に挙げることができる。ビフェニルテトラカルボン酸二無水物以外のテトラカルボン酸成分を用いる場合、なかでも、得られるポリイミドの特性から、４，４’－オキシジフタル酸二無水物、またはピロメリット酸二無水物を用いることが特に好ましい。前述のテトラカルボン酸二無水物は一種である必要はなく、複数種の混合物であっても構わない。 In the present invention, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride may be used in an amount of 50 mol% or less, or a tetracarboxylic acid component other than biphenyltetracarboxylic dianhydride (tetra Carboxylic dianhydride) may be used in the range of 50 mol% or less. The tetracarboxylic dianhydride that can be used in combination with biphenyltetracarboxylic dianhydride in the present invention is not particularly limited, but aromatic tetracarboxylic dianhydrides and alicyclic rings are obtained from the properties of the resulting polyimide. The formula tetracarboxylic dianhydride is preferred. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, p-terphenyl tetracarboxylic dianhydride Anhydrous, m-terphenyltetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc. are preferred Can be mentioned. When using a tetracarboxylic acid component other than biphenyltetracarboxylic dianhydride, it is particularly preferable to use 4,4′-oxydiphthalic dianhydride or pyromellitic dianhydride because of the characteristics of the resulting polyimide. preferable. The tetracarboxylic dianhydride described above need not be one kind, and may be a mixture of plural kinds.
　本発明で用いることができるジアミンとしては、特に限定するものではないが、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルメタン、３，３’－ジクロロベンジジン、４，４’－ジアミノジフェニルスルフィド、３，３’－ジアミノジフェニルスルホン、１，５－ジアミノナフタレン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、３，３’－ジメチル－４，４’－ビフェニルジアミン、ベンジジン、３，３’－ジメチルベンジジン、３，３’－ジメトキシベンジジン、４，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルプロパン、２，４－ジアミノトルエン、ビス（４－アミノ－３－カルボキシフェニル）メタン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、ビス〔４－（４－アミノフェノキシ）フェニル〕スルホン、２，４－ビス（β－アミノ－第三ブチル）トルエン、ビス（ｐ－β－アミノ－第三ブチルフェニル）エーテル、ビス（ｐ－β－メチル－６－アミノフェニル）ベンゼン、ビス－ｐ－（１，１－ジメチル－５－アミノ－ペンチル）ベンゼン、１－イソプロピル－２，４－ｍ－フェニレンジアミン、ｍ－キシリレンジアミン、ｐ－キシリレンジアミン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、４，４’－メチレンビス（２，６－キシリジン）、α，α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼンなどの芳香族ジアミン、ジ（ｐ－アミノシクロヘキシル）メタン、１，４－ジアミノシクロヘキサンなどの脂環式構造を含むジアミン、へキサメチレンジアミン、へプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ジアミノプロピルテトラメチレン、３－メチルヘプタメチレンジアミン、４，４－ジメチルヘプタメチレンジアミン、２，１１－ジアミノドデカン、１，２－ビス－３－アミノプロポキシエタン、２，２－ジメチルプロピレンジアミン、３－メトキシヘキサメチレンジアミン、２，５－ジメチルヘキサメチレンジアミン、２，５－ジメチルヘプタメチレンジアミン、３－メチルへプタメチレンジアミン、５－メチルノナメチレンジアミン、２，１７－ジアミノエイコサデカン、１，１０－ジアミノ－１，１０－ジメチルデカン、１，１２－ジアミノオクタデカンなどの脂肪族ジアミン等を好適に挙げることができる。前述のジアミンは一種である必要はなく、複数種の混合物であっても構わない。 The diamine that can be used in the present invention is not particularly limited. 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine , Benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylpropane, 2,4-diaminotoluene, bis (4-amino- 3-carboxyphenyl) methane, 1,3-bis (4-amino) Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2 , 4-bis (β-amino-tert-butyl) toluene, bis (p-β-amino-tert-butylphenyl) ether, bis (p-β-methyl-6-aminophenyl) benzene, bis-p- ( 1,1-dimethyl-5-amino-pentyl) benzene, 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 4,4′-methylenebis (2,6-xylidine), α, α′-bis (4-aminophenyl) -1,4-diisopropylben Aromatic diamines such as diamine, diamines containing alicyclic structures such as di (p-aminocyclohexyl) methane, 1,4-diaminocyclohexane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Decamethylenediamine, diaminopropyltetramethylene, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropylene Diamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 2,17-diaminoeicosadeca , 1,10-diamino-1,10-dimethyl decane, may be mentioned suitably 1,12 aliphatic diamines such as diamino-octadecane and the like. The aforementioned diamine need not be a single type, and may be a mixture of a plurality of types.
　上記のうち、芳香族ジアミンとして、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、２，４－ジアミノトルエン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、ｍ－キシリレンジアミン、ｐ－キシリレンジアミン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、４，４’－メチレンビス（２，６－キシリジン）、α，α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼンがより好ましく、脂肪族ジアミンとして、へキサメチレンジアミン、へプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ジアミノプロピルテトラメチレン、３－メチルヘプタメチレンジアミン、２，１１－ジアミノドデカン、１，１２－ジアミノオクタデカンがより好ましい。なかでも、得られるポリイミドの特性から、ｐ－フェニレンジアミン、または４，４’－ジアミノジフェニルエーテルのいずれか一種以上を用いることが特に好ましい。 Among the above, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 1,3-bis (4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, m-xylylenediamine, p-xylylenediamine, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-methylenebis (2,6-xylidine), α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene More preferably, as the aliphatic diamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine More preferred are nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylene, 3-methylheptamethylenediamine, 2,11-diaminododecane, and 1,12-diaminooctadecane. Among these, it is particularly preferable to use at least one of p-phenylenediamine and 4,4′-diaminodiphenyl ether from the characteristics of the obtained polyimide.
　本発明で用いるポリアミック酸は、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できることが必要である。特に水蒸気透過係数が１．８ｇ・ｍｍ／（ｍ2・２４ｈ）以上のポリイミドフィルムを製造できることが好ましい。得られるポリイミドフィルムの水蒸気透過係数がこれより小さい値である場合、ポリイミド絶縁被覆層の製造において、急速な昇温による短時間の熱処理によりイミド化を行おうとすると、部分的な結晶化を起こし易い。 The polyamic acid used in the present invention can produce a polyimide film having a water vapor transmission coefficient larger than 1.7 g · mm / (m 2 · 24 h) by heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C. is required. In particular, it is preferable that a polyimide film having a water vapor transmission coefficient of 1.8 g · mm / (m 2 · 24 h) or more can be produced. When the water vapor permeability coefficient of the resulting polyimide film is smaller than this, partial crystallization is likely to occur if imidization is attempted by a short heat treatment with rapid temperature increase in the production of a polyimide insulating coating layer. .
　ここで、イミド化過程における結晶化について説明する。イミド化過程においては、溶媒の蒸発とイミド化反応が平行して起こる。昇温速度が大きいと、イミド化反応の進行に対して溶媒の蒸発量が少なくなり、残存溶媒量が比較的多くなる。ポリアミック酸のイミド化が進行してイミド結合が生成すると、分子鎖の溶媒に対する溶解性が小さくなる。そのため、残存溶媒量が比較的多い状態では、分子鎖が結晶化して析出しやすくなる。一方、昇温速度が小さい場合、イミド化反応の進行に対して溶媒の蒸発量が多くなり、残存溶媒が少ないため、結晶化が起こりにくい。本発明のポリイミド前駆体組成物に用いるポリアミック酸からは気体を透過しやすいポリイミド樹脂が得られるため、溶媒が蒸発し易く、昇温速度が大きい条件における結晶化の問題が起こりにくくなる。 Here, crystallization in the imidization process will be described. In the imidization process, solvent evaporation and imidization reaction occur in parallel. When the rate of temperature increase is large, the amount of solvent evaporation decreases with the progress of the imidization reaction, and the amount of residual solvent increases relatively. As the imidization of the polyamic acid proceeds and an imide bond is generated, the solubility of the molecular chain in the solvent decreases. Therefore, in a state where the amount of residual solvent is relatively large, the molecular chain is easily crystallized and precipitated. On the other hand, when the rate of temperature rise is low, the amount of solvent evaporation increases with the progress of the imidization reaction, and the residual solvent is small, so that crystallization hardly occurs. Since the polyamic acid used in the polyimide precursor composition of the present invention provides a polyimide resin that is easily permeable to gas, the solvent is likely to evaporate, and the problem of crystallization under conditions where the rate of temperature increase is high is less likely to occur.
　最高加熱温度を３００～５００℃とする条件下で加熱処理することにより得られるポリイミドフィルムの水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリアミック酸としては、例えば、テトラカルボン酸成分として２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含むポリアミック酸が挙げられる。この場合、ジアミン成分として、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはそのいずれか一方を５０～１００モル％含むことが好ましい。 Examples of polyamic acid having a water vapor transmission coefficient larger than 1.7 g · mm / (m 2 · 24 h) of the polyimide film obtained by heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C. include, for example, tetracarboxylic acid Examples of the acid component include polyamic acid containing 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. In this case, the diamine component preferably contains 50 to 100 mol% of paraphenylenediamine and 4,4′-diaminodiphenyl ether, or any one of them.
　また、前記ポリアミック酸としては、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分として、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含むポリアミック酸が挙げられる。 The polyamic acid contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, and paraphenylenediamine, 4,4 ′ as a diamine component. Comprising at least one diamine selected from the group consisting of 2-diaminodiphenyl ether and 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, and comprising 2,2′-bis [4- (4-amino And polyamic acid containing 30 to 100 mol% of phenoxy) phenyl] propane.
　さらに、前記ポリアミック酸としては、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分として、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含むポリアミック酸が挙げられる。 Further, the polyamic acid includes 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, 4,4′-diaminodiphenyl ether as a diamine component, and Polyamic acid comprising one or more diamines selected from the group consisting of 4,4′-methylenebis (2,6-xylidine) and containing 20 to 100 mol% of 4,4′-methylenebis (2,6-xylidine) Is mentioned.
　本発明で用いるポリアミック酸は、略等モルのテトラカルボン酸二無水物とジアミンとを、溶媒中で、イミド化反応を抑制するために１００℃以下、好ましくは８０℃以下の比較的低温で反応させることにより、ポリアミック酸溶液として得ることができる。 The polyamic acid used in the present invention reacts with an approximately equimolar amount of tetracarboxylic dianhydride and diamine in a solvent at a relatively low temperature of 100 ° C. or lower, preferably 80 ° C. or lower in order to suppress the imidization reaction. By making it, it can be obtained as a polyamic acid solution.
　限定するものではないが、通常、反応温度は２５℃～１００℃、好ましくは４０℃～８０℃、より好ましくは５０℃～８０℃であり、反応時間は０．１～２４時間程度、好ましくは２～１２時間程度である。反応温度及び反応時間を前記範囲内とすることによって、生産効率よく高分子量のポリアミック酸溶液を容易に得ることができる。 Although not limited, the reaction temperature is usually 25 ° C. to 100 ° C., preferably 40 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C., and the reaction time is about 0.1 to 24 hours, preferably About 2 to 12 hours. By setting the reaction temperature and the reaction time within the above ranges, a high molecular weight polyamic acid solution can be easily obtained with high production efficiency.
　なお、反応は、空気雰囲気下でも行うことができるが、通常は不活性ガス、好ましくは窒素ガス雰囲気下で好適に行われる。 The reaction can be carried out in an air atmosphere, but is usually suitably carried out in an inert gas, preferably a nitrogen gas atmosphere.
　略等モルのテトラカルボン酸二無水物とジアミンとは、具体的には、これらのモル比［テトラカルボン酸二無水物／ジアミン］で０．９０～１．１０程度、好ましくは０．９５～１．０５程度である。 The approximately equimolar tetracarboxylic dianhydride and diamine are specifically about 0.90 to 1.10, preferably 0.95 to about their molar ratio [tetracarboxylic dianhydride / diamine]. It is about 1.05.
　本発明で用いる溶媒としては、ポリアミック酸を重合可能であればいずれの溶媒でもよく、水溶媒であっても、有機溶媒であってもよい。溶媒は２種以上の混合物であってもよく、２種以上の有機溶媒の混合溶媒、又は水と１種以上の有機溶媒の混合溶媒も好適に用いることができる。 The solvent used in the present invention may be any solvent as long as it can polymerize polyamic acid, and may be an aqueous solvent or an organic solvent. The solvent may be a mixture of two or more, and a mixed solvent of two or more organic solvents or a mixed solvent of water and one or more organic solvents can also be suitably used.
　本発明で用いることができる有機溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン、Ｎ－メチルカプロラクタム、ヘキサメチルホスホロトリアミド、１，２－ジメトキシエタン、ビス（２－メトキシエチル）エーテル、１，２－ビス（２－メトキシエトキシ）エタン、テトラヒドロフラン、ビス［２－（２－メトキシエトキシ）エチル］エーテル、１，４－ジオキサン、ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソール、ｍ－クレゾール、フェノール、γ－ブチロラクトンなどが挙げられる。 The organic solvent that can be used in the present invention is not particularly limited. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N— Ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethylurea, anisole, m -Cresol, phenol, - butyrolactone, and the like.
　なお、この反応に用いた溶媒が、本発明のポリイミド前駆体組成物に含まれる溶媒であることができる。 In addition, the solvent used for this reaction can be a solvent contained in the polyimide precursor composition of the present invention.
　本発明で用いるポリアミック酸は、限定されないが、温度３０℃、濃度０．５ｇ／１００ｍＬで測定した対数粘度が０．２以上、好ましくは０．４以上、特に好ましくは０．６以上であることが好適である。対数粘度が前記範囲よりも低い場合には、ポリアミック酸の分子量が低いことから、高い特性のポリイミドを得ることが難しくなることがある。 The polyamic acid used in the present invention is not limited, but the logarithmic viscosity measured at a temperature of 30 ° C. and a concentration of 0.5 g / 100 mL is 0.2 or more, preferably 0.4 or more, particularly preferably 0.6 or more. Is preferred. When the logarithmic viscosity is lower than the above range, it may be difficult to obtain a polyimide having high characteristics because the molecular weight of the polyamic acid is low.
　本発明で用いるポリイミド前駆体組成物は、ポリアミック酸に起因する固形分濃度が、限定されないが、ポリアミック酸と溶媒との合計量に対して、好ましくは５質量％～４５質量％、より好ましくは５質量％～４０質量％、さらに好ましくは５質量％超～３０質量％であることが好適である。固形分濃度が５質量％より低いと使用時の取り扱いが悪くなることがあり、４５質量％より高いと溶液の流動性がなくなることがある。 The polyimide precursor composition used in the present invention is not limited in the solid content concentration due to the polyamic acid, but is preferably 5% by mass to 45% by mass, more preferably based on the total amount of the polyamic acid and the solvent. The content is preferably 5% by mass to 40% by mass, more preferably more than 5% by mass and 30% by mass. When the solid content concentration is lower than 5% by mass, handling during use may be deteriorated, and when it is higher than 45% by mass, the fluidity of the solution may be lost.
　また、本発明で用いるポリイミド前駆体組成物の３０℃における溶液粘度は、限定されないが、好ましくは１０００Ｐａ・ｓｅｃ以下、より好ましくは０．５～５００Ｐａ・ｓｅｃ、さらに好ましくは１～３００Ｐａ・ｓｅｃ、特に好ましくは２～２００Ｐａ・ｓｅｃであることが取り扱い上好適である。 The solution viscosity at 30 ° C. of the polyimide precursor composition used in the present invention is not limited, but is preferably 1000 Pa · sec or less, more preferably 0.5 to 500 Pa · sec, still more preferably 1 to 300 Pa · sec, Particularly preferably, the pressure is 2 to 200 Pa · sec.
　ポリイミド前駆体組成物は、加熱処理によって溶媒を除去するとともにイミド化（脱水閉環）することによってポリイミドとなるが、上記のような本発明のポリイミド前駆体組成物を用いることにより、ポリイミド絶縁被覆層の形成のために、短時間で昇温し高温で焼付ける工程を採用することが可能となる。ここで、短時間で昇温して高温で焼付けをするとは、例えば、ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、且つ、１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上となる条件で昇温し、最高加熱温度が３００～５００℃である工程である。 The polyimide precursor composition is converted into polyimide by removing the solvent by heat treatment and imidizing (dehydrating ring closure). By using the polyimide precursor composition of the present invention as described above, a polyimide insulating coating layer is obtained. Therefore, it is possible to employ a process of raising the temperature in a short time and baking at a high temperature. Here, when the temperature is increased in a short time and baking is performed at a high temperature, for example, the time for heating the polyimide precursor composition is 10 to 180 seconds, and the average temperature increase rate from 100 ° C. to 280 ° C. In this process, the temperature is raised under the condition of 5 ° C./s or more, and the maximum heating temperature is 300 to 500 ° C.
　本発明では、公知の方法により基材に上記のようなポリイミド前駆体組成物を塗布し、加熱（焼付け）することによりポリイミド絶縁被覆層を形成する。この焼付け工程においては、ポリイミド前駆体組成物を加熱する時間（加熱炉で加熱する場合、加熱炉内にある時間）を１０～１８０秒間とし、１００℃から２８０℃までの平均昇温速度を５℃／ｓ以上とし、最高加熱温度を３００～５００℃とすることができる。１００℃から２８０℃までの平均昇温速度の上限は、特に限定されないが、例えば、５０℃／ｓ以下が好ましい。 In the present invention, the polyimide precursor composition as described above is applied to a substrate by a known method, and heated (baked) to form a polyimide insulating coating layer. In this baking step, the time for heating the polyimide precursor composition (when heated in a heating furnace, the time in the heating furnace) is 10 to 180 seconds, and the average temperature increase rate from 100 ° C. to 280 ° C. is 5 The maximum heating temperature can be 300 to 500 ° C. The upper limit of the average rate of temperature increase from 100 ° C. to 280 ° C. is not particularly limited, but for example, 50 ° C./s or less is preferable.
　本発明においては、さらに、１００℃から３００℃までの平均昇温速度を５℃／ｓ以上（すなわち、１００℃～３００℃まで４０秒以内）としてもよく、１００℃から最高加熱温度（３００～５００℃）までの平均昇温速度を５℃／ｓ以上としてもよい。１００℃までの平均昇温速度も、特に限定されないが、５℃／ｓ以上としてもよい。 In the present invention, the average rate of temperature increase from 100 ° C. to 300 ° C. may be 5 ° C./s or more (ie, from 100 ° C. to 300 ° C. within 40 seconds). The average rate of temperature increase up to 500 ° C. may be 5 ° C./s or more. The average rate of temperature increase up to 100 ° C. is not particularly limited, but may be 5 ° C./s or more.
　本発明においては、１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上（すなわち、１００℃～２８０℃まで３６秒以内）であれば、室温から最高加熱温度までの昇温条件に制限はなく、一定の昇温速度で昇温してもよく、また加熱処理中に昇温速度を変更してもよく、段階的に昇温してもよい。 In the present invention, if the average rate of temperature increase from 100 ° C. to 280 ° C. is 5 ° C./s or more (that is, within 36 seconds from 100 ° C. to 280 ° C.), the temperature is increased from room temperature to the maximum heating temperature. There is no limitation, the temperature may be raised at a constant rate of temperature rise, the rate of temperature rise may be changed during the heat treatment, and the temperature may be raised stepwise.
　このイミド化のための加熱処理は、例えば、空気雰囲気下、あるいは不活性ガス雰囲気下で行うことができる。 The heat treatment for imidization can be performed, for example, in an air atmosphere or an inert gas atmosphere.
　なお、上記以外の条件で、本発明のポリイミド前駆体組成物を加熱処理してポリイミド絶縁被覆層を形成することもできる。 It should be noted that the polyimide insulating coating layer can also be formed by heat-treating the polyimide precursor composition of the present invention under conditions other than those described above.
　なお、基材は、特に限定されず、用途に応じて適宜選択される。また、形成するポリイミド絶縁被覆層の厚みも、特に限定されず、用途に応じて適宜選択される。 In addition, a base material is not specifically limited, According to a use, it selects suitably. Further, the thickness of the polyimide insulating coating layer to be formed is not particularly limited, and is appropriately selected according to the application.
　本発明により得られるポリイミド絶縁被覆層は、高度の耐電圧性、耐熱性、及び耐湿熱性を有する絶縁部材（被覆層）である。したがって、電気・電子部品関連、自動車分野、航空宇宙分野等に特に好適に使用でき、ＨＶ車モーター用コイルや超小型モーターの分野にも使用可能である。 The polyimide insulating coating layer obtained by the present invention is an insulating member (coating layer) having high voltage resistance, heat resistance, and moist heat resistance. Therefore, it can be particularly suitably used in the fields of electric / electronic parts, the automobile field, the aerospace field, etc., and can also be used in the fields of coils for HV car motors and micro motors.
　以下、本発明を実施例により更に具体的に説明するが、本発明は、これら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
　以下の例で用いた特性の測定方法を以下に示す。
＜固形分濃度＞
　試料溶液（その質量をｗ1とする）を、熱風乾燥機中１２０℃で１０分間、２５０℃で１０分間、次いで３５０℃で３０分間加熱処理して、加熱処理後の質量（その質量をｗ2とする）を測定する。固形分濃度［質量％］は、次式によって算出した。 A method for measuring the characteristics used in the following examples is shown below.
<Concentration of solid content>
The sample solution (whose mass is w 1 ) was heat-treated in a hot air dryer at 120 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 30 minutes. 2 ). Solid content concentration [mass%] was computed by the following formula.
　　　　固形分濃度［質量％］＝（ｗ2／ｗ1）×１００
＜溶液粘度（回転粘度）＞
　トキメック社製Ｅ型粘度計を用いて３０℃で測定した。
＜絶縁被覆層の状態観察（被覆膜評価）＞
　得られた被覆層について目視により状態観察を行った。濁りが全くないものを良好、濁りがある領域が１０％を越えているものを濁りありとした。「濁りがある」ということは、ポリイミド樹脂が少なくとも一部結晶化していることを示している。
＜昇温速度の測定＞
　被覆層形成工程において、キーエンス株式会社製の計測ユニットＮＲ－ＴＨ０８と解析ソフトＷＡＶＥ　ＬＯＧＧＥＲを用いて、サンプル温度が１００℃から２８０℃に変化するまでの所要時間を測定した。
＜水蒸気透過係数＞
　ＪＩＳ Ｋ７１２９のＢ法に準拠して、４０℃、相対湿度９０％で測定を行った。
＜弾性率、引張強度、引張伸度＞
　調製したポリイミド前駆体組成物をガラス基板上に塗工し、熱風オーブン中、８０℃で３０分加熱し、続いて３５０℃で３０分加熱して硬化させ、厚さがおよそ２５μｍのポリイミドフィルムを作製した。得られたポリイミドフィルムを幅１０ｍｍ、長さ１００ｍｍに切り出して試験片とした。この試験片について、引張試験機（オリエンテック製；テンシロンＲＴＧ－１２２５）を使用して、温度２５℃、湿度５０％ＲＨ、クロスヘッド速度５０ｍｍ／分、チャック間距離５０ｍｍの条件で、引張弾性率、引張強度、及び引張伸度を測定した。 Solid content concentration [% by mass] = (w 2 / w 1 ) × 100
<Solution viscosity (rotational viscosity)>
It measured at 30 degreeC using the Tokimec E-type viscosity meter.
<Insulation coating state observation (coating film evaluation)>
The state of the obtained coating layer was visually observed. A sample having no turbidity was judged good and a turbid region exceeding 10% was designated as turbid. The phrase “has turbidity” indicates that the polyimide resin is at least partially crystallized.
<Measurement of heating rate>
In the coating layer forming step, the time required for the sample temperature to change from 100 ° C. to 280 ° C. was measured using a measurement unit NR-TH08 manufactured by Keyence Corporation and analysis software WAVE LOGGER.
<Water vapor transmission coefficient>
Based on JIS K7129 method B, the measurement was performed at 40 ° C. and relative humidity 90%.
<Elastic modulus, tensile strength, tensile elongation>
The prepared polyimide precursor composition is coated on a glass substrate, heated in a hot air oven at 80 ° C. for 30 minutes, and then cured by heating at 350 ° C. for 30 minutes to form a polyimide film having a thickness of about 25 μm. Produced. The obtained polyimide film was cut into a width of 10 mm and a length of 100 mm to obtain a test piece. For this test piece, using a tensile testing machine (Orientec; Tensilon RTG-1225) under the conditions of temperature 25 ° C., humidity 50% RH, crosshead speed 50 mm / min, and distance between chucks 50 mm. , Tensile strength, and tensile elongation were measured.
　以下の例で使用した化合物の略号について説明する。
ｓ－ＢＰＤＡ：３，３’，４，４’－ビフェニルテトラカルボン酸二無水物
ａ-ＢＰＤＡ：２，３，３’，４’－ビフェニルテトラカルボン酸二無水物
ＯＤＡ：４，４’－ジアミノジフェニルエーテル
ＰＰＤ：ｐ－フェニレンジアミン
ＢＡＰＰ：２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン
ＭＤＸ：４，４’－メチレンビス（２，６－キシリジン）
ＮＭＰ：Ｎ－メチル－２－ピロリドン The abbreviations of the compounds used in the following examples are described.
s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride a-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride ODA: 4,4′-diamino Diphenyl ether PPD: p-phenylenediamine BAPP: 2,2′-bis [4- (4-aminophenoxy) phenyl] propane MDX: 4,4′-methylenebis (2,6-xylidine)
NMP: N-methyl-2-pyrrolidone
〔実施例１〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Example 1]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 396 g of NMP was added as a solvent, and 40.05 g (0.2 mol) of ODA was added thereto. Stir for hours to dissolve. To this solution, 58.84 g (0.2 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.5% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を、膜厚５０μｍのポリイミドフィルム上に塗工した。得られたサンプルを事前に３８０℃に熱したＳＵＳ板の上に置いて１分間保持し、厚さがおよそ２５μｍの絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 This polyimide precursor composition was coated on a polyimide film having a thickness of 50 μm. The obtained sample was placed on a SUS plate previously heated to 380 ° C. and held for 1 minute to form an insulating coating layer having a thickness of approximately 25 μm. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔実施例２〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４７．０８ｇ（０．１６モル）、ａ－ＢＰＤＡの１１．７７ｇ（０．０４モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Example 2]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 396 g of NMP was added as a solvent, and 40.05 g (0.2 mol) of ODA was added thereto. Stir for hours to dissolve. To this solution, 47.08 g (0.16 mol) of s-BPDA and 11.77 g (0.04 mol) of a-BPDA were added and stirred at 50 ° C. for 3 hours to obtain a solid concentration of 18.5% by mass. A polyimide precursor composition having a solution viscosity of 5.0 Pa · s was obtained.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔比較例１〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５２．９６ｇ（０．１８モル）、ａ－ＢＰＤＡの５．８８ｇ（０．０２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 1]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 396 g of NMP was added as a solvent, and 40.05 g (0.2 mol) of ODA was added thereto. Stir for hours to dissolve. To this solution, 52.96 g (0.18 mol) of s-BPDA and 5.88 g (0.02 mol) of a-BPDA were added and stirred at 50 ° C. for 3 hours to obtain a solid content concentration of 18.5% by mass. A polyimide precursor composition having a solution viscosity of 5.0 Pa · s was obtained.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔比較例２〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 2]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 396 g of NMP was added as a solvent, and 40.05 g (0.2 mol) of ODA was added thereto. Stir for hours to dissolve. To this solution, 58.84 g (0.2 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.5% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔実施例３〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にａ－ＢＰＤＡの７０．６１ｇ（０．２４モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 Example 3
386 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.95 g (0.24 mol) of PPD was added thereto. Stir for hours to dissolve. 70.61 g (0.24 mol) of a-BPDA was added to this solution, and the mixture was stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.2% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔実施例４〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの３５．３１ｇ（０．１２モル）、ａ－ＢＰＤＡの３５．３１ｇ（０．１２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 Example 4
386 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.95 g (0.24 mol) of PPD was added thereto. Stir for hours to dissolve. To this solution, 35.31 g (0.12 mol) of s-BPDA and 35.31 g (0.12 mol) of a-BPDA were added and stirred at 50 ° C. for 3 hours to obtain a solid concentration of 18.2% by mass. A polyimide precursor composition having a solution viscosity of 5.0 Pa · s was obtained.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔比較例３〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４２．３７ｇ（０．１４モル）、ａ－ＢＰＤＡの２８．２５ｇ（０．１０モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 3]
386 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.95 g (0.24 mol) of PPD was added thereto. Stir for hours to dissolve. To this solution, 42.37 g (0.14 mol) of s-BPDA and 28.25 g (0.10 mol) of a-BPDA were added, followed by stirring at 50 ° C. for 3 hours to obtain a solid content concentration of 18.2% by mass. A polyimide precursor composition having a solution viscosity of 5.0 Pa · s was obtained.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔比較例４〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの７０．６１ｇ（０．２４モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 4]
386 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.95 g (0.24 mol) of PPD was added thereto. Stir for hours to dissolve. To this solution, 70.61 g (0.24 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.2% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). With respect to the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 1.
〔実施例５〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９５ｇを加え、これにＢＡＰＰの５７．４７ｇ（０．１４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４１．１９ｇ（０．１４モル）を加え、５０℃で３時間撹拌して、固形分濃度１９．０質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 Example 5
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 395 g of NMP was added as a solvent, and 57.47 g (0.14 mol) of BAPP was added thereto. Stir for hours to dissolve. To this solution, 41.19 g (0.14 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 19.0% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔実施例６〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４０１ｇを加え、これにＢＡＰＰの２２．１７ｇ（０．０５モル）、ＯＤＡの２５．２３ｇ（０．１３モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５２．９６ｇ（０．１８モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．７質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 Example 6
401 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, to which 22.17 g (0.05 mol) of BAPP and 25.23 g of ODA ( 0.13 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 52.96 g (0.18 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.7% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔比較例５〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＢＡＰＰの１４．７８ｇ（０．０４モル）、ＯＤＡの２８．８３ｇ（０．１４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５２．９６ｇ（０．１８モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．７質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 5]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 386 g of NMP was added as a solvent, and 14.78 g (0.04 mol) of BAPP and 28.83 g of ODA ( 0.14 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 52.96 g (0.18 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.7% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔実施例７〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９３ｇを加え、これにＢＡＰＰの４５．９８ｇ（０．１１モル）、ＰＰＤの５．１９ｇ（０．０５モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４７．０８ｇ（０．１６モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．８質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 Example 7
To a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, 393 g of NMP was added as a solvent, and 45.98 g (0.11 mol) of BAPP and 5.19 g of PPD ( 0.05 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. 47.08 g (0.16 mol) of s-BPDA was added to this solution and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.8% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔比較例６〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９７ｇを加え、これにＢＡＰＰの４１．８７ｇ（０．１０モル）、ＰＰＤの７．３５ｇ（０．０７モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５０．０２ｇ（０．１７モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．８質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 6]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 397 g of NMP was added as a solvent, and 41.87 g (0.10 mol) of BAPP and 7.35 g of PPD ( 0.07 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 50.02 g (0.17 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.8% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔実施例８〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４０４ｇを加え、これにＭＤＸの１０．１８ｇ（０．０４モル）、ＯＤＡの３２．０４ｇ（０．１６モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．６質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 Example 8
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 404 g of NMP was added as a solvent, and 10.18 g (0.04 mol) of MDX and 32.04 g of ODA ( 0.16 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 58.84 g (0.2 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.6% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔比較例７〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＭＤＸの５．０９ｇ（０．０２モル）、ＯＤＡの３６．０４ｇ（０．１８モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２０モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．６質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 7]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 400 g of NMP was added as a solvent, and 5.09 g (0.02 mol) of MDX and 36.04 g of ODA ( 0.18 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 58.84 g (0.20 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid content concentration of 18.6% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔比較例８〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９２ｇを加え、これにＭＤＸの３０．５３ｇ（０．１２モル）、ＰＰＤの８．６５ｇ（０．０８モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 8]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge pipe, 392 g of NMP was added as a solvent, and 30.53 g (0.12 mol) of MDX and 8.65 g of PPD ( 0.08 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 58.84 g (0.2 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.5% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
〔比較例９〕
　攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９９ｇを加え、これにＭＤＸの２６．７１ｇ（０．１１モル）、ＰＰＤの１１．３５ｇ（０．１１モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの６１．７９ｇ（０．２１モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。 [Comparative Example 9]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 399 g of NMP was added as a solvent, and 26.71 g (0.11 mol) of MDX and 11.35 g of PPD ( 0.11 mol) was added and stirred at 50 ° C. for 1 hour to dissolve. To this solution, 61.79 g (0.21 mol) of s-BPDA was added and stirred at 50 ° C. for 3 hours to obtain a polyimide precursor composition having a solid concentration of 18.5% by mass and a solution viscosity of 5.0 Pa · s. Got.
　このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 An insulation coating layer was prepared in the same manner as in Example 1 using this polyimide precursor composition. In this case, the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s). Regarding the obtained polyimide precursor composition and insulating coating layer, the results of state observation and property evaluation are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (8)

  1. 　ポリアミック酸と溶媒とを含むポリイミド前駆体組成物であって、
    　前記ポリアミック酸が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸であり、かつ、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものであることを特徴とする、ポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。     A polyimide precursor composition comprising a polyamic acid and a solvent,
    The polyamic acid comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or any one of 50 to 100 A polyamic acid obtained from a tetracarboxylic acid component and a diamine component contained in a mol%, and when subjected to heat treatment under conditions where the maximum heating temperature is 300 to 500 ° C., the water vapor transmission coefficient is 1.7 g · mm / A polyimide precursor composition for forming a polyimide insulating coating layer, which is capable of producing a polyimide film larger than (m 2 · 24h).
  2. 　テトラカルボン酸成分が、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含み、
    　ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、請求項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。     The tetracarboxylic acid component comprises 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride,
    The polyimide precursor composition for forming a polyimide insulating coating layer according to claim 1, wherein the diamine component contains paraphenylenediamine and 4,4'-diaminodiphenyl ether, or 50 to 100 mol% of any one of them.
  3. 　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、
    　ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、請求項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。     The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
    The diamine component comprises one or more diamines selected from the group consisting of paraphenylenediamine, 4,4′-diaminodiphenyl ether and 2,2′-bis [4- (4-aminophenoxy) phenyl] propane. The polyimide precursor composition for forming a polyimide insulating coating layer according to claim 1, comprising 30 to 100 mol% of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane.
  4. 　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、
    　ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、請求項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。     The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
    The diamine component comprises one or more diamines selected from the group consisting of 4,4′-diaminodiphenyl ether and 4,4′-methylenebis (2,6-xylidine), and 4,4′-methylenebis (2,6 The polyimide precursor composition for forming a polyimide insulating coating layer according to claim 1, comprising 20 to 100 mol% of xylidine).
  5. 　基材にポリイミド前駆体組成物を塗布、焼付けする工程を有するポリイミド絶縁被覆層の製造方法であって、
    　ポリイミド前駆体組成物が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸を含み、かつ、このポリアミック酸が、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものであり、
    　焼付け工程において、
    ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、
    １００℃から２８０℃までの平均昇温速度が５℃／ｓ以上であり、
    最高加熱温度が３００～５００℃であることを特徴とする絶縁被覆層の製造方法。     A method for producing a polyimide insulating coating layer comprising a step of applying and baking a polyimide precursor composition on a substrate,
    The polyimide precursor composition contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, or 50 of them. A water vapor transmission coefficient is obtained by heat treatment under the condition that the polyamic acid is obtained from a tetracarboxylic acid component and a diamine component contained in an amount of ˜100 mol% and the maximum heating temperature is 300 to 500 ° C. Is capable of producing a polyimide film of greater than 1.7 g · mm / (m 2 · 24 h),
    In the baking process,
    The time for heating the polyimide precursor composition is 10 to 180 seconds,
    The average rate of temperature increase from 100 ° C. to 280 ° C. is 5 ° C./s or more,
    A method for producing an insulating coating layer, wherein the maximum heating temperature is 300 to 500 ° C.
  6. 　テトラカルボン酸成分が、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含み、
    　ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、請求項５に記載の絶縁被覆層の製造方法。     The tetracarboxylic acid component comprises 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride,
    6. The method for producing an insulating coating layer according to claim 5, wherein the diamine component contains 50 to 100 mol% of paraphenylenediamine and 4,4′-diaminodiphenyl ether, or any one of them.
  7. 　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、
    　ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、請求項５に記載の絶縁被覆層の製造方法。     The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
    The diamine component comprises one or more diamines selected from the group consisting of paraphenylenediamine, 4,4′-diaminodiphenyl ether and 2,2′-bis [4- (4-aminophenoxy) phenyl] propane. The method for producing an insulating coating layer according to claim 5, comprising 30 to 100 mol% of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane.
  8. 　テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、
    　ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、請求項５に記載の絶縁被覆層の製造方法。
     
          The tetracarboxylic acid component contains 50 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
    The diamine component comprises one or more diamines selected from the group consisting of 4,4′-diaminodiphenyl ether and 4,4′-methylenebis (2,6-xylidine), and 4,4′-methylenebis (2,6 The method for producing an insulating coating layer according to claim 5, comprising 20 to 100 mol% of xylidine).

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