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WO2016056595A1 - Composition de précurseur de polyimide et procédé de production d'une couche de revêtement isolant l'utilisant - Google Patents

Composition de précurseur de polyimide et procédé de production d'une couche de revêtement isolant l'utilisant 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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English (en)
Japanese (ja)
Inventor
武史 寺田
剛成 中山
圭吾 長尾
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Ube Corp
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Ube Industries Ltd
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Priority to JP2016553136A priority Critical patent/JP7242157B2/ja
Publication of WO2016056595A1 publication Critical patent/WO2016056595A1/fr
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Priority to JP2022212592A priority patent/JP7635775B2/ja
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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.

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

Abstract

La présente invention se rapporte à une composition de précurseur de polyimide utilisable en vue de la formation d'une couche de revêtement isolant à base de polyimide, composition caractérisée en ce qu'elle permet la production d'un film de polyimide qui comprend un solvant et un acide polyamique obtenu à partir d'un composant diamine et d'un composant acide tétracarboxylique contenant 50 à 100 % en moles de dianhydride 3,3',4,4'-biphényltétracarboxylique et/ou de dianhydride 2,3,3',4'-biphényltétracarboxylique, et le film de polyimide présentant un coefficient de perméation de vapeur supérieur à 1,7 g·mm/(m2·24H) suite à la mise en œuvre d'un traitement thermique de l'acide polyamique dans des conditions telles à ce que la température de chauffage maximale varie de 300 à 500° C.
PCT/JP2015/078502 2014-10-08 2015-10-07 Composition de précurseur de polyimide et procédé de production d'une couche de revêtement isolant l'utilisant Ceased WO2016056595A1 (fr)

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JP2017203113A (ja) * 2016-05-12 2017-11-16 宇部興産株式会社 絶縁被覆層の製造方法
CN112457492A (zh) * 2020-11-27 2021-03-09 桂林电器科学研究院有限公司 低热膨胀系数热塑性聚酰亚胺、薄膜、模塑粉及制备方法
CN113088076A (zh) * 2019-12-23 2021-07-09 中国科学院宁波材料技术与工程研究所 一种高性能聚酰亚胺模塑粉、其制备方法与应用
WO2021176779A1 (fr) * 2020-03-03 2021-09-10 昭和電工マテリアルズ株式会社 Précurseur de polyamide, composition de résine et substrat souple

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WO2016056595A1 (fr) * 2014-10-08 2016-04-14 宇部興産株式会社 Composition de précurseur de polyimide et procédé de production d'une couche de revêtement isolant l'utilisant
KR102359568B1 (ko) 2016-08-05 2022-02-08 신에쓰 가가꾸 고교 가부시끼가이샤 열전도성 실리콘 고무 복합 시트

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JP2017203113A (ja) * 2016-05-12 2017-11-16 宇部興産株式会社 絶縁被覆層の製造方法
CN113088076A (zh) * 2019-12-23 2021-07-09 中国科学院宁波材料技术与工程研究所 一种高性能聚酰亚胺模塑粉、其制备方法与应用
CN113088076B (zh) * 2019-12-23 2022-09-06 中国科学院宁波材料技术与工程研究所 一种高性能聚酰亚胺模塑粉、其制备方法与应用
WO2021176779A1 (fr) * 2020-03-03 2021-09-10 昭和電工マテリアルズ株式会社 Précurseur de polyamide, composition de résine et substrat souple
WO2021176560A1 (fr) * 2020-03-03 2021-09-10 昭和電工マテリアルズ株式会社 Précurseur de polyamide pour fil isolé, composition de résine pour fil isolé et fil isolé
CN112457492A (zh) * 2020-11-27 2021-03-09 桂林电器科学研究院有限公司 低热膨胀系数热塑性聚酰亚胺、薄膜、模塑粉及制备方法
CN112457492B (zh) * 2020-11-27 2022-11-04 桂林电器科学研究院有限公司 低热膨胀系数热塑性聚酰亚胺、薄膜、模塑粉及制备方法

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