WO2016121817A1 - Composition de précurseur de polyimide, et procédé de production d'une couche de revêtement isolant faisant appel à celle-ci - Google Patents

Composition de précurseur de polyimide, et procédé de production d'une couche de revêtement isolant faisant appel à celle-ci Download PDF

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WO2016121817A1
WO2016121817A1 PCT/JP2016/052344 JP2016052344W WO2016121817A1 WO 2016121817 A1 WO2016121817 A1 WO 2016121817A1 JP 2016052344 W JP2016052344 W JP 2016052344W WO 2016121817 A1 WO2016121817 A1 WO 2016121817A1
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Prior art keywords
polyimide
precursor composition
polyamic acid
coating layer
polyimide precursor
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PCT/JP2016/052344
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English (en)
Japanese (ja)
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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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Priority to JP2016572103A priority Critical patent/JP6760083B2/ja
Publication of WO2016121817A1 publication Critical patent/WO2016121817A1/fr

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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • H01B17/60—Composite insulating bodies
    • 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 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 relates to a polyamic acid which is a combination of a tetracarboxylic acid component and a diamine component, which easily gives crystalline polyimide, and in particular, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component. It is an object of the present invention to provide a method for forming a polyimide insulating coating layer without imperfection even if rapid temperature rise is performed in a method for producing a polyimide insulating coating layer by imidizing polyamic acid using a polyamic acid. To do.
  • the present invention provides a polyimide precursor composition (polyamic acid composition) capable of forming a polyimide resin insulation coating layer having excellent heat resistance and mechanical properties in a short time without causing crystallization.
  • Another object of the present invention is to provide an industrially advantageous method for producing an insulating coating layer using the same.
  • a polyimide precursor composition comprising a polyamic acid, a solvent, and a phosphorus compound,
  • the polyamic acid contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, and their total content is
  • a polyamic acid obtained from a tetracarboxylic acid component of 50 to 100 mol% and a diamine component containing 50 to 100 mol% of 4,4′-diaminodiphenyl ether;
  • the phosphorus compound is at least one selected from the group consisting of a phosphate ester and a phosphorus compound represented by the following general formula (1),
  • the polyamic acid is capable of producing a polyimide film having a water vapor transmission coefficient larger than 1.0 g ⁇ mm / (m 2 ⁇ 24 h) by heat treatment under conditions where the maximum heating temperature is 300 to 500
  • R 1 is an alkylene group having 1 to 6 carbon atoms, and R 2 is a phenyl group or a cyclohexyl group.
  • 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 includes a polyamic acid, a solvent, and a phosphorus compound
  • the polyamic acid contained in the polyimide precursor composition includes 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride.
  • the phosphorus compound is at least one selected from the group consisting of a phosphate ester and a phosphorus compound represented by the following general formula (1),
  • the polyamic acid can produce a polyimide film having a water vapor transmission coefficient larger than 1.0 g ⁇ mm / (m 2 ⁇ 24 h) by heat treatment under conditions where 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,
  • a polyimide insulation coating layer, a polyimide layer, a polyimide coating, and a polyimide film refer to what consists mainly of a polyimide, and the thing containing phosphorus etc. is also contained.
  • 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.
  • an insulating coating layer of a polyimide resin 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 it is possible to form a highly reliable insulating coating layer that is particularly suppressed in thermal decomposition at high temperatures and excellent in adhesive strength with a substrate. .
  • 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 is characterized by using a specific polyamic acid that gives a polyimide film having a specific water vapor transmission coefficient, and further adding a specific phosphorus compound.
  • 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.
  • This polyamic acid is obtained from a tetracarboxylic acid component containing 50 to 100 mol% of biphenyltetracarboxylic dianhydride and a diamine component containing 50 to 100 mol% of 4,4′-diaminodiphenyl ether.
  • 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.
  • the polyamic acid is heated at a maximum heating temperature of 300 to 500 ° C., and in particular, the temperature is raised from room temperature (25 ° C.) to 400 ° C. over 30 minutes.
  • a polyimide film having a water vapor transmission coefficient larger than 1.0 g ⁇ mm / (m 2 ⁇ 24 h) can be produced.
  • the tetracarboxylic acid component used in the present invention includes 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride,
  • the total content of is preferably 50 to 100 mol%.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in an amount of 50 mol% or more.
  • biphenyltetracarboxylic acid other than 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is used as the tetracarboxylic acid component.
  • 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, which is an acid dianhydride may be used within a range of 50 mol% or less, or a tetracarboxylic acid other than biphenyltetracarboxylic dianhydride You may use a component (tetracarboxylic dianhydride) in 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.
  • 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.
  • 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 component used in the present invention contains 50 to 100 mol% of 4,4′-diaminodiphenyl ether, and other diamines can be used in the range of 50 mol% or less.
  • Other diamines include, but are not limited to, 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 Aromatics such as [4- (4-aminophenoxy) phenyl] propane, 4,4′-methylenebis (2,6-xylidine), ⁇ , ⁇ ′-bis (4-aminophenyl) -1
  • the polyamic acid used in the present invention is heated at a maximum heating temperature of 300 to 500 ° C., and in particular, the temperature is raised from room temperature (25 ° C.) to 400 ° C. over 30 minutes. It is necessary to be able to produce a polyimide film having a water vapor transmission coefficient larger than 1.0 g ⁇ mm / (m 2 ⁇ 24 h) by heat treatment for 10 minutes. In particular, it is preferable that a polyimide film having a water vapor transmission coefficient larger than 1.2 g ⁇ mm / (m 2 ⁇ 24 h) can be produced. If the water vapor transmission coefficient of the resulting polyimide film is smaller than this, partial crystallization will occur when imidization is performed by a short heat treatment with rapid temperature rise in the production of the polyimide insulation coating layer. easy.
  • 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.
  • Examples of the polyamic acid having a water vapor transmission coefficient larger than 1.0 g ⁇ mm / (m 2 ⁇ 24 h) of the polyimide film obtained by heat treatment under a condition where the maximum heating temperature is 300 to 500 ° C. include, for example, 3, A tetracarboxylic acid component composed of 3 ', 4,4'-biphenyltetracarboxylic dianhydride and 2,3,3', 4'-biphenyltetracarboxylic dianhydride, and 4,4'-diaminodiphenyl ether A polyamic acid composed of a diamine component is preferred.
  • the content of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the tetracarboxylic acid component is 95 to 50 mol%, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. More preferably, the dianhydride content is 5 to 50 mol%.
  • 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 preferably has a logarithmic viscosity of 0.2 or more measured at a temperature of 30 ° C. and a concentration of 0.5 g / 100 mL.
  • a 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 50% by mass, more preferably based on the total amount of the polyamic acid and the solvent. It is suitable to be 5% by mass to 45% by mass, more preferably 10% by mass to 45% by mass, and still more preferably more than 15% by mass to 40% by mass.
  • 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.
  • 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 of the present invention contains a phosphorus compound in addition to a polyamic acid and a solvent. Addition of the phosphorus compound suppresses thermal decomposition of the formed polyimide insulating coating layer at a high temperature, and also improves the adhesive strength with the substrate.
  • the phosphorus compound used in the present invention is preferably selected from the group consisting of a phosphate ester and a phosphorus compound represented by the following chemical formula (1).
  • R 1 is an alkylene group having 1 to 6 carbon atoms
  • R 2 is a phenyl group or a cyclohexyl group.
  • R 1 in the chemical formula (1) is preferably an alkylene group having 1 to 4 carbon atoms.
  • phosphorus compounds represented by the chemical formula (1) bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, Examples include 1,4-bis (diphenylphosphino) butane and 1,4-bis (dicyclohexylphosphino) butane.
  • the phosphoric acid ester is derived from phosphoric acid and alcohol, and the structure is not particularly limited.
  • the phosphate ester used in the present invention may be any of monoester, diester and triester, but is preferably derived from an aliphatic or aromatic alcohol having 1 to 18 carbon atoms. Monoesters and diesters may form salts with amines and the like.
  • phosphate esters include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and phosphate ester compounds represented by the following chemical formula (2) and salts thereof.
  • Examples of the compound that forms a salt with the phosphate ester compound represented by the following chemical formula (2) include an amine represented by the following chemical formula (3).
  • R 3 is a hydrogen atom, an alkyl group having 6 to 18 carbon atoms or a polyoxyethylene group, and R 4 is an alkyl group having 6 to 18 carbon atoms or a polyoxyethylene group.
  • R 5 , R 6 and R 7 are a hydrogen atom, a hydroxyethyl group or an alkyl group having 1 to 4 carbon atoms.
  • phosphate ester compound represented by following Chemical formula (4) can also be mentioned as phosphate ester used by this invention.
  • R 8 is a C 3-12 organic group having a reactive functional group.
  • R 8 in the chemical formula (4) is a reactive functional group, specifically, an organic group having 3 to 12 carbon atoms having a carbon-carbon unsaturated bond, and R 8 includes acryloyl group, methacryloyl group, acryloyloxy, and the like. Examples thereof include an ethyl group and a methacryloyloxyethyl group.
  • phosphate ester compound represented by the chemical formula (4) examples include 2- (methacryloyloxy) ethyl phosphate and bis (2- (methacryloyloxy) ethyl phosphate).
  • these phosphorus compounds may be used alone or in combination of two or more. Further, other phosphorus compounds may be used in combination.
  • the addition amount of the phosphorus compound in the polyimide precursor composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the mass of the polyamic acid.
  • concentration of the phosphorus compound in the polyimide precursor composition is too small, it becomes difficult to sufficiently obtain the effect of suppressing thermal decomposition in a temperature range of 400 ° C. or higher.
  • concentration of the phosphorus compound is too high, a large amount of phosphorus remains in the resulting polyimide insulation coating layer, which may cause volatile components (outgas), which is not preferable.
  • the phosphorus compound may be added before or after the polyamic acid is prepared. That is, after the tetracarboxylic acid component and the diamine component are reacted in a solvent to obtain a polyamic acid solution, a phosphorus compound is added thereto to obtain the polyimide precursor composition of the present invention containing the phosphorus compound. Can do. Also, the polyimide precursor of the present invention containing a phosphorus compound can be obtained by adding a tetracarboxylic acid component, a diamine component, and a phosphorus compound to a solvent and reacting the tetracarboxylic acid component and the diamine component in the solvent in the presence of the phosphorus compound. A body composition can be obtained.
  • 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.
  • a polyimide insulating coating layer is formed by applying a polyimide precursor composition containing a polyamic acid, a solvent and a phosphorus compound as described above to a substrate by a known method and heating (baking).
  • 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.
  • 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.
  • s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride
  • ODA 4,4′-diamino Diphenyl ether
  • NMP N-methyl-2-pyrrolidone
  • DPPE 1,2-bis (diphenylphosphino) ethane
  • TEP triethyl phosphate
  • Example 1 To a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, 300 g of NMP was added as a solvent, 60.08 g (0.3 mol) of ODA was added thereto, and the mixture was stirred at 50 ° C. for 1 hour, Dissolved. To this solution were added 70.61 g (0.24 mol) of s-BPDA, 17.65 g (0.06 mol) of a-BPDA, and 1.62 g (0.09 mol) of water, and the mixture was stirred at 50 ° C. for 3 hours.
  • a polyimide precursor composition having a partial concentration of 30.6% by mass and a solution viscosity of 7.0 Pa ⁇ s was obtained.
  • 3.37 g of DPPE 0.75% by mass with respect to the composition and 2.27% by mass with respect to the mass of polyamic acid
  • a phosphorus compound was added as a phosphorus compound to obtain a polyimide precursor composition.
  • This polyimide precursor composition was applied onto a polyimide film having a thickness of 50 ⁇ m, placed on a SUS plate heated to 350 ° C., and held for 1 minute to form an insulating coating layer (polyimide coating).
  • the sample temperature was raised from 100 ° C. to 280 ° C. for 12 seconds (heating rate 15 ° C./s).
  • Table 1 shows the evaluation results of state observation of the obtained insulating coating layer.
  • this polyimide precursor composition was applied on a glass plate as a substrate, heated from room temperature to 400 ° C. over 30 minutes, and heat-treated at 400 ° C. for 10 minutes to obtain a polyimide film having a thickness of 25 ⁇ m. It was.
  • the obtained polyimide coating (polyimide film) was peeled from the substrate, and the water vapor transmission coefficient and the weight change during heating at 490 ° C. were measured. The evaluation results are shown in Table 1.
  • this polyimide precursor composition was applied on a smooth surface of a copper foil having a thickness of 18 ⁇ m (manufactured by Mitsui Kinzoku Mining Co., Ltd., 3EC-VLP) so that the thickness of the resulting polyimide layer was 25 ⁇ m.
  • the temperature was raised to 30 ° C. over 30 minutes, and heat treatment was performed at 400 ° C. for 10 minutes to obtain a laminate.
  • the adhesive strength between a polyimide layer and copper foil was measured. The evaluation results are shown in Table 1.
  • Example 2 A polyimide precursor composition was prepared in the same manner as in Example 1 except that 6.74 g of DPPE (1.5% by mass with respect to the composition and 4.54% by mass with respect to the mass of polyamic acid) was used as the phosphorus compound. Then, the insulation coating layer on the polyimide film, the polyimide film, and the laminate composed of the polyimide layer and the copper foil were manufactured, and the state observation and the measurement / evaluation of the characteristics were performed. In addition, the temperature increase rate from 100 degreeC to 280 degreeC in manufacture of the insulating coating layer on a polyimide film was 15 degreeC / s. The results are shown in Table 1.
  • Example 3 3.37 g of JPA-514 (mixture of 2- (methacryloyloxy) ethyl phosphate and bis (2- (methacryloyloxy) ethyl phosphate)) manufactured by Johoku Chemical Co., Ltd. as a phosphorus compound (0.75 to the composition)
  • the polyimide precursor composition was prepared in the same manner as in Example 1 except that 2 mass% and 2.27 mass% based on the mass of the polyamic acid were used, and the production of an insulating coating layer on the polyimide film, the polyimide film And a laminate composed of a polyimide layer and a copper foil were prepared, and the state was observed and the characteristics were measured and evaluated.
  • the temperature increase rate from 100 degreeC to 280 degreeC in manufacture of the insulating coating layer on a polyimide film was 15 degreeC / s. The results are shown in Table 1.
  • Example 4 A polyimide precursor in the same manner as in Example 1 except that 6.74 g of JPA-514 (1.5% by mass with respect to the composition and 4.54% by mass with respect to the mass of the polyamic acid) was used as the phosphorus compound.
  • the composition was prepared, and the insulation coating layer on the polyimide film, the polyimide film, and the laminate composed of the polyimide layer and the copper foil were manufactured, and the state observation and the measurement / evaluation of the properties were performed.
  • the temperature increase rate from 100 degreeC to 280 degreeC in manufacture of the insulating coating layer on a polyimide film was 15 degreeC / s. The results are shown in Table 1.
  • Example 5 A polyimide precursor composition in the same manner as in Example 1 except that 3.37 g of TEP (0.75% by mass with respect to the composition and 2.27% by mass with respect to the mass of the polyamic acid) was used as the phosphorus compound. was prepared, and the insulation coating layer on the polyimide film was manufactured, the polyimide film was manufactured, and the laminate composed of the polyimide layer and the copper foil was manufactured, and the state was observed and the characteristics were measured and evaluated. In addition, the temperature increase rate from 100 degreeC to 280 degreeC in manufacture of the insulating coating layer on a polyimide film was 15 degreeC / s. The results are shown in Table 1.
  • Example 6 A polyimide precursor composition in the same manner as in Example 1 except that 6.74 g of TEP (1.5% by mass with respect to the composition and 4.54% by mass with respect to the mass of the polyamic acid) was used as the phosphorus compound. was prepared, and the insulation coating layer on the polyimide film was manufactured, the polyimide film was manufactured, and the laminate composed of the polyimide layer and the copper foil was manufactured, and the state was observed and the characteristics were measured and evaluated. In addition, the temperature increase rate from 100 degreeC to 280 degreeC in manufacture of the insulating coating layer on a polyimide film was 15 degreeC / s. The results are shown in Table 1.
  • Example 1 A polyimide precursor composition was prepared in the same manner as in Example 1 except that no phosphorus compound was added, and the production of an insulating coating layer on the polyimide film, the production of the polyimide film, and the laminate comprising the polyimide layer and the copper foil Manufacture was performed, state observation and measurement / evaluation of characteristics were performed. In addition, the temperature increase rate from 100 degreeC to 280 degreeC in manufacture of the insulating coating layer on a polyimide film was 15 degreeC / s. The results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de précurseur de polyimide permettant de former des couches de revêtement isolant de polyimide, caractérisée en ce qu'elle comprend un acide polyamique spécifique et un composé phosphoré spécifique. La composition est en outre caractérisée en ce que l'acide polyamique est un acide qui, une fois chauffé dans des conditions telles que la température de chauffage maximale est de 300 à 500 °C, peut produire un film de polyimide présentant un coefficient de perméabilité à la vapeur d'eau supérieur à 1,0 g·mm/ (m2·24h).
PCT/JP2016/052344 2015-01-29 2016-01-27 Composition de précurseur de polyimide, et procédé de production d'une couche de revêtement isolant faisant appel à celle-ci WO2016121817A1 (fr)

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JP2018116850A (ja) * 2017-01-18 2018-07-26 住友電気工業株式会社 絶縁電線及びその製造方法
KR20230066346A (ko) 2020-09-10 2023-05-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 중합체 조성물, 바니시, 및 폴리이미드 필름
KR20230066345A (ko) 2020-09-10 2023-05-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 중합체 조성물, 바니시, 및 폴리이미드 필름

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JPH08230101A (ja) * 1995-02-28 1996-09-10 Ube Ind Ltd 金属箔積層のポリイミドフィルム
JPH08244168A (ja) * 1995-03-09 1996-09-24 Ube Ind Ltd 金属箔積層ポリイミドフィルムの製造法
JPH0940775A (ja) * 1995-08-01 1997-02-10 Ube Ind Ltd ポリイミドフィルム
JP2000043211A (ja) * 1998-07-31 2000-02-15 Ube Ind Ltd 接着性の改良されたポリイミドフィルム、その製法および積層体
JP2006321981A (ja) * 2005-04-20 2006-11-30 Toyobo Co Ltd 接着シート、金属積層シートおよびプリント配線板
JP2014142173A (ja) * 2012-12-27 2014-08-07 Mitsubishi Alum Co Ltd 内面螺旋溝付管およびその製造方法と熱交換器
JP2014210894A (ja) * 2013-04-22 2014-11-13 宇部興産株式会社 ポリアミック酸溶液組成物、及びそれを用いたポリイミド膜の製造方法

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JPH08230101A (ja) * 1995-02-28 1996-09-10 Ube Ind Ltd 金属箔積層のポリイミドフィルム
JPH08244168A (ja) * 1995-03-09 1996-09-24 Ube Ind Ltd 金属箔積層ポリイミドフィルムの製造法
JPH0940775A (ja) * 1995-08-01 1997-02-10 Ube Ind Ltd ポリイミドフィルム
JP2000043211A (ja) * 1998-07-31 2000-02-15 Ube Ind Ltd 接着性の改良されたポリイミドフィルム、その製法および積層体
JP2006321981A (ja) * 2005-04-20 2006-11-30 Toyobo Co Ltd 接着シート、金属積層シートおよびプリント配線板
JP2014142173A (ja) * 2012-12-27 2014-08-07 Mitsubishi Alum Co Ltd 内面螺旋溝付管およびその製造方法と熱交換器
JP2014210894A (ja) * 2013-04-22 2014-11-13 宇部興産株式会社 ポリアミック酸溶液組成物、及びそれを用いたポリイミド膜の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018116850A (ja) * 2017-01-18 2018-07-26 住友電気工業株式会社 絶縁電線及びその製造方法
KR20230066346A (ko) 2020-09-10 2023-05-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 중합체 조성물, 바니시, 및 폴리이미드 필름
KR20230066345A (ko) 2020-09-10 2023-05-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 중합체 조성물, 바니시, 및 폴리이미드 필름

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