WO2014041816A1 - Stratifié de polyimide transparent et son procédé de fabrication - Google Patents

Stratifié de polyimide transparent et son procédé de fabrication Download PDF

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Publication number
WO2014041816A1
WO2014041816A1 PCT/JP2013/005438 JP2013005438W WO2014041816A1 WO 2014041816 A1 WO2014041816 A1 WO 2014041816A1 JP 2013005438 W JP2013005438 W JP 2013005438W WO 2014041816 A1 WO2014041816 A1 WO 2014041816A1
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Prior art keywords
transparent polyimide
transparent
group
polyimide
film
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PCT/JP2013/005438
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English (en)
Japanese (ja)
Inventor
佳広 坂田
健一 福川
真喜 岡崎
浦上　達宣
敦 大久保
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三井化学株式会社
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Priority to KR1020157003920A priority Critical patent/KR101692648B1/ko
Priority to JP2014535384A priority patent/JP6265902B2/ja
Priority to CN201380043084.0A priority patent/CN104582960B/zh
Publication of WO2014041816A1 publication Critical patent/WO2014041816A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a transparent polyimide laminate and a method for producing the same.
  • Polyimide resin has excellent heat resistance and mechanical properties, and polyimide film is applied to various flexible printed circuit boards.
  • One method for producing a polyimide film is a casting method.
  • the casting method includes (i) applying a polyimide precursor on a supporting substrate, (ii) imidizing the polyimide precursor by heat treatment, (iii) peeling the polyimide film from the supporting substrate, How to get.
  • the supporting base material is generally a glass substrate, but it has also been proposed that the supporting base material be a metal plate or a non-thermoplastic resin (Patent Documents 1 to 3).
  • inorganic glass which is a transparent material, is used for panel substrates and the like.
  • inorganic glass has a high specific gravity (weight), and further has low flexibility and impact resistance. Therefore, films made of PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) are widely used for substrates such as liquid crystal display elements and organic EL display elements that require flexibility.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • these films have low heat resistance, and the temperature at the time of forming various elements is limited. Therefore, a substrate having higher heat resistance is required.
  • Patent Document 4 a polyimide film obtained by reacting bis (trifluoromethyl) benzidine with a tetracarboxylic acid component has been proposed as a film having both high transparency and heat resistance.
  • the polyimide film of Patent Document 4 produced by the casting method is difficult to peel from the support substrate (glass substrate), and in order to peel the polyimide film, the support substrate and the polyimide film are immersed in water. In other words, it is necessary to irradiate the interface between the supporting substrate and the polyimide film with laser light.
  • An object of this invention is to provide the transparent polyimide laminated body which has a transparent polyimide layer with high light transmittance, a small in-plane phase difference, and which can be easily peeled from a support base material, and its manufacturing method.
  • 1st of this invention is related with the manufacturing method of the following transparent polyimide laminated bodies.
  • a method for producing a transparent polyimide laminate comprising a supporting substrate and a transparent polyimide layer laminated on the supporting substrate, wherein a) a polyimide precursor obtained by reacting a tetracarboxylic acid component and a diamine component A step of coating a polyimide precursor-containing solution containing a body and a solvent on the support substrate; and b) a glass transition of the transparent polyimide layer with a polyimide precursor film comprising a coating film of the polyimide precursor-containing solution.
  • the transparent polyimide layer has a glass transition temperature of 260 ° C.
  • [2] The method for producing a transparent polyimide laminate according to [1], wherein the support substrate is a flexible substrate.
  • [3] The method for producing a polyimide laminate according to [1] or [2], wherein a release agent is further included in the polyimide precursor-containing solution.
  • [4] The method for producing a transparent polyimide laminate according to any one of [1] to [3], wherein the oxygen concentration of the atmosphere is 5% by volume or less in the temperature range exceeding 200 ° C. in the step b).
  • [5] The method for producing a transparent polyimide laminate according to any one of [1] to [3], wherein the atmosphere is depressurized in the temperature range exceeding 200 ° C. in the step b).
  • the step b) is a step of heating the polyimide precursor film while raising the temperature from 150 ° C. or lower to over 200 ° C., and the average temperature rising rate in the temperature range of 150 to 200 ° C. in the step b)
  • the polyimide precursor includes a tetracarboxylic acid component (A) containing at least one tetracarboxylic dianhydride represented by the following general formula (a), and the following general formulas (b-1) to (The compound according to any one of [1] to [6], which is a compound obtained by reacting a diamine component (B) containing one or more diamines selected from the group consisting of compounds represented by b-3): A method for producing a transparent polyimide laminate.
  • R 1 represents a tetravalent group having 4 to 27 carbon atoms, and an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, or a monocyclic aromatic group.
  • a condensed polycyclic aromatic group, a non-condensed polycyclic aliphatic group in which the cycloaliphatic groups are linked directly or by a bridging member, or an aromatic group is directly or a bridging member Represents non-condensed polycyclic aromatic groups linked together by
  • R 10 represents a tetravalent group having 4 to 27 carbon atoms, and an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, or a monocyclic aromatic group.
  • a condensed polycyclic aromatic group, a non-condensed polycyclic aliphatic group in which the cycloaliphatic groups are linked directly or by a bridging member, or an aromatic group is directly or a bridging member Represents non-condensed polycyclic aromatic groups linked together by
  • the polyimide precursor is composed of a polyamic acid block composed of a repeating structural unit represented by the following general formula (G) and a polyimide block composed of a repeating structural unit represented by the following general formula (H)
  • R 7 is a divalent group having 4 to 51 carbon atoms, and an aliphatic group, a monocyclic aliphatic group (excluding a 1,4-cyclohexylene group), a condensed group A polycyclic aliphatic group, a monocyclic aromatic group or a condensed polycyclic aromatic group, or a non-condensed polycyclic aliphatic group in which the cyclic aliphatic groups are connected to each other directly or by a bridging member Or a non-condensed polycyclic aromatic group in which the aromatic
  • the step a) is a step of applying the polyimide precursor-containing solution onto the support substrate fed out from a roll, and the step b) is performed after the polyimide precursor film is heated.
  • 2nd of this invention is related with the following transparent polyimide laminated bodies and optical films.
  • [11] A transparent polyimide laminate obtained from the production method according to any one of [1] to [9].
  • 3rd of this invention is related with the manufacturing method of a transparent polyimide film, the manufacturing method of a flexible device, and various display apparatuses.
  • a method for producing a transparent polyimide film comprising a step of peeling the transparent polyimide layer from the support substrate of the transparent polyimide laminate according to [11] to obtain a transparent polyimide film.
  • a method for producing a flexible device comprising a step of forming an element on a transparent polyimide film obtained by the production method according to [11].
  • a touch panel display obtained by the method for producing a flexible device according to [14] or [15].
  • a liquid crystal display obtained by the method for producing a flexible device according to [14] or [15].
  • An organic EL display obtained by the method for producing a flexible device according to [14] or [15].
  • a transparent polyimide laminate having a transparent polyimide layer that can be easily peeled off from a supporting substrate, has high light transmittance, and has a small in-plane retardation.
  • FIG. 1 is a side view showing an example of a production apparatus for producing a long transparent polyimide laminate by the production method of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a method for producing a flexible device using the transparent polyimide laminate of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another example of a method for producing a flexible device using the transparent polyimide laminate of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing another example of a method for producing a flexible device using the transparent polyimide laminate of the present invention.
  • the manufacturing method of a transparent polyimide laminated body is a transparent polyimide laminated body containing a support base material and a transparent polyimide layer, Comprising:
  • the peel strength at the time of peeling a transparent polyimide layer from a support base material is 0.
  • a transparent polyimide laminate having a range of 005 to 0.20 kN / m, preferably 0.01 to 0.15 kN / m, and more preferably 0.05 to 0.10 kN / m is produced.
  • the peel strength is a value measured according to JIS C-6471 (peeling angle 90 °).
  • the peel strength between the transparent polyimide layer and the supporting substrate is small. Therefore, even after an element is formed on the transparent polyimide layer, the transparent polyimide layer can be easily peeled from the support substrate.
  • the manufacturing method of the present invention includes the following two steps. a) A step of applying a polyimide precursor-containing solution containing a polyimide precursor obtained by reacting a tetracarboxylic acid component and a diamine component and a solvent onto a supporting substrate. b) A coating film of the polyimide precursor-containing solution. The process of heating the polyimide precursor film above the glass transition temperature of the transparent polyimide layer
  • the transparent polyimide laminate of the present invention can be produced as a long transparent polyimide laminate 30 using, for example, the apparatus shown in FIG.
  • the manufacturing apparatus shown in FIG. 1 includes a polyimide precursor coating device 20, an endless belt 21, and a plurality of heating furnaces 10 arranged along the moving direction of the endless belt 21.
  • a polyimide precursor is applied to the supporting base material 11 unwound from the roll by a coating device 20 to form a coating film 1 of the polyimide precursor.
  • the coating film 1 of a polyimide precursor is imidized with the heating furnace 10, and the transparent polyimide laminated body on which the support base material 11 and transparent polyimide layer 1 'were laminated
  • Step a) A polyimide precursor-containing solution containing a polyimide precursor obtained by reacting a tetracarboxylic acid component and a diamine component and a solvent is prepared.
  • the type of polyimide precursor contained in the polyimide precursor-containing solution is not particularly limited, but from the viewpoint of increasing the total light transmittance of the resulting transparent polyimide layer, the main chain of the polyimide precursor contains an alicyclic group. It is preferred that The polyimide precursor containing solution containing such a polyimide precursor will be described in detail later.
  • the prepared polyimide precursor-containing solution is applied onto the support substrate.
  • the supporting substrate is not particularly limited as long as it has solvent resistance and heat resistance.
  • the support substrate is preferably one having good peelability of the resulting transparent polyimide layer, and is preferably a flexible substrate made of a metal or a heat-resistant polymer film.
  • flexible substrates made of metal include copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, silicon, bismuth , Indium, or a metal foil made of an alloy thereof.
  • a release agent may be coated on the surface of the metal foil.
  • examples of the flexible substrate made of a heat resistant polymer film include a polyimide film, an aramid film, a polyether ether ketone film, and a polyether ether sulfone film.
  • the flexible substrate made of a heat-resistant polymer film may contain a release agent or an antistatic agent, and may be coated with a release agent or an antistatic agent on the surface. It is preferable that the supporting substrate is a polyimide film because the peelability from the obtained transparent polyimide layer is good and the heat resistance and solvent resistance are high.
  • the ten-point average roughness (Rz) of the surface of the support substrate is preferably less than 0.4 ⁇ m, more preferably 0.2 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the ten-point average roughness (Rz) of the surface of the supporting substrate is a value measured according to JIS B-0601, and is a value measured in the width direction of the supporting substrate.
  • the surface of the supporting substrate is free from defects such as adhesion of foreign matters and streak-like scratches. Even if the ten-point average roughness (Rz) is low, the haze of the obtained transparent polyimide layer tends to increase when these defects are present in the support substrate.
  • the defects on the surface of the supporting substrate can be evaluated by “the number of defects per unit area”. Defects are confirmed by visual observation.
  • the number of defects contained per support substrate 210 mm ⁇ 297 mm (A4 size) is usually preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.
  • the shape of the supporting substrate is appropriately selected according to the shape of the transparent polyimide laminate to be produced, and may be a single-leaf sheet or a long shape.
  • the thickness of the supporting substrate is preferably 5 to 150 ⁇ m, more preferably 10 to 70 ⁇ m. When the thickness of the supporting substrate is less than 5 ⁇ m, wrinkles may be generated on the supporting substrate or the supporting substrate may be torn during application of the polyimide precursor-containing solution.
  • the polyimide precursor-containing solution to the support substrate is not particularly limited as long as the polyimide precursor-containing solution can be applied with a constant film thickness.
  • the coating apparatus include a die coater, a comma coater, a roll coater, a gravure coater, a curtain coater, a spray coater, and a lip coater.
  • the thickness (coating thickness) of the polyimide precursor-containing solution is appropriately selected according to the desired thickness of the transparent polyimide layer and the concentration of the polyimide precursor in the polyimide precursor-containing solution.
  • Step b) the polyimide precursor-containing solution coating film formed on the supporting substrate in Step a) described above; that is, the polyimide precursor film is heated. Specifically, i) the polyimide precursor film is heated while increasing the temperature from 150 ° C. or lower to over 200 ° C., and ii) the temperature (constant temperature) equal to or higher than the glass transition temperature of the obtained transparent polyimide layer. Thus, it is preferable to be a step of heating for a certain time.
  • the temperature at which a general polyimide precursor is imidized is 150 to 200 ° C. Therefore, when the temperature of the polyimide precursor film is rapidly increased to 200 ° C. or higher, the polyimide precursor on the coating film surface is imidized before the solvent is volatilized from the polyimide precursor film. And when the solvent in a coating film foams or a solvent is discharge
  • the temperature rise may be continuous or stepwise (sequential), but it is preferable to be continuous from the viewpoint of suppressing the appearance defect of the obtained transparent polyimide layer. Moreover, in the above-mentioned whole temperature range, the temperature increase rate may be constant or may be changed in the middle.
  • An example of a method of heating a single-leaf polyimide precursor film while raising the temperature includes a method of raising the temperature in the oven for heating the polyimide precursor film.
  • the heating rate is adjusted by the oven setting.
  • a heating furnace 10 for heating the polyimide precursor film 1 is transported to the support base 11 ( A plurality of them are arranged along the (moving) direction; the temperature of the heating furnace 10 is changed for each heating furnace 10. For example, what is necessary is just to raise the temperature of each heating furnace 10 along the moving direction of the support base material 11.
  • FIG. In this case, the temperature increase rate is adjusted by the conveyance speed of the support substrate 11.
  • the polyimide precursor film is further heated at a temperature (constant temperature) equal to or higher than the glass transition temperature of the transparent polyimide layer obtained.
  • the temperature at this time is not particularly limited as long as it is equal to or higher than the glass transition temperature of the transparent polyimide layer to be obtained, but is more preferably a temperature higher by 5 to 30 ° C. than the glass transition temperature of the transparent polyimide layer to be obtained, and more preferably the obtained transparent
  • the temperature is 5 to 20 ° C. higher than the glass transition temperature of the polyimide layer.
  • the polyimide precursor can be sufficiently imidized by heating at a temperature equal to or higher than the glass transition temperature of the obtained transparent polyimide layer for a certain time.
  • a transparent polyimide layer softens and the solvent inside a transparent polyimide layer fully volatilizes.
  • the heating time at a temperature equal to or higher than the glass transition temperature is appropriately selected according to the heating temperature, the thickness of the polyimide precursor film, the amount of solvent contained in the polyimide precursor-containing solution, and the like. Usually about 0.5 to 2 hours.
  • the heating method for heating the polyimide precursor film at a constant temperature is not particularly limited.
  • the polyimide precursor film is heated in an oven adjusted to a constant temperature.
  • the long polyimide precursor film is heated in a heating furnace or the like that maintains a constant temperature.
  • Polyimide is easily oxidized when heated at a temperature exceeding 200 ° C.
  • the transparent polyimide layer obtained turns yellow, and the total light transmittance of the transparent polyimide layer decreases. Therefore, in a temperature range exceeding 200 ° C., it is preferable that (i) the oxygen concentration of the heating atmosphere is 5% by volume or less, or (ii) the heating atmosphere is decompressed.
  • the oxygen concentration in the heating atmosphere is 5% by volume or less, the oxidation reaction of polyimide is suppressed.
  • the oxygen concentration in the temperature region exceeding 200 ° C. is more preferably 3% by volume or less, and further preferably 1% by volume or less.
  • a method for reducing the oxygen concentration is not particularly limited, and may be a method of introducing an inert gas into the heating atmosphere.
  • the oxygen concentration in the atmosphere is measured by a commercially available oxygen concentration meter (for example, a zirconia oxygen concentration meter).
  • the oxidation reaction of polyimide is also suppressed by reducing the heating atmosphere.
  • the pressure in the atmosphere is preferably 5 kPa or less, more preferably 1 kPa or less.
  • the polyimide precursor film is heated in a vacuum oven or the like.
  • Step b) The imidation ratio of the transparent polyimide layer at the end of heating is preferably 90% or more, more preferably 93% or more, and still more preferably 95% or more. If the imidization ratio is less than 90%, imidization proceeds when the transparent polyimide layer is used, and moisture may be released from the transparent polyimide layer.
  • the imidization rate can be calculated from the measured value of the IR absorption spectrum of the transparent polyimide layer. Specifically, it is calculated by the following method.
  • the amount of solvent remaining in the transparent polyimide layer is preferably 1.0% by mass or less, more preferably 0. 0.8 mass% or less, more preferably 0.5 mass% or less. If the residual amount of the solvent exceeds 1.0% by mass, the solvent may be released from the transparent polyimide layer when the transparent polyimide layer is used.
  • the residual amount of solvent is specified by peeling the transparent polyimide layer from the support substrate, pyrolyzing the transparent polyimide layer with an electric furnace type pyrolysis furnace, etc., and analyzing the pyrolyzed components with a gas chromatography mass spectrometer To do.
  • a step of winding the transparent polyimide laminate to form a roll as described above may be performed.
  • a polyimide precursor containing solution contains a polyimide precursor and a solvent, and if necessary, a release agent.
  • a release agent is contained in the polyimide precursor-containing solution, the peelability between the transparent polyimide layer and the support substrate in the transparent polyimide laminate is increased.
  • various additives may be contained in the polyimide precursor containing solution as needed.
  • Polyimide precursor The polyimide precursor is obtained by reacting a tetracarboxylic acid component (A) with a diamine component (B).
  • concentration of the polyimide precursor contained in the polyimide precursor-containing solution is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
  • concentration of a polyimide precursor exceeds 50 mass%, the viscosity of a polyimide precursor containing solution will become high too much, and the application
  • it is less than 5% by mass the viscosity of the polyimide precursor-containing solution is excessively low, and the polyimide precursor film may not be applied to a desired thickness. Moreover, it takes time to dry the solvent, and the production efficiency of the polyimide film is deteriorated.
  • Tetracarboxylic acid component (A) The tetracarboxylic acid component (A) constituting the polyimide precursor includes a tetracarboxylic dianhydride represented by the following general formula (a).
  • the tetracarboxylic acid component (A) may contain only one type of tetracarboxylic dianhydride represented by the general formula (a), or may contain two or more types.
  • R 1 represents a tetravalent organic group having 4 to 27 carbon atoms.
  • R 1 represents an aliphatic group; a monocyclic aliphatic group; a condensed polycyclic aliphatic group; a monocyclic aromatic group; a condensed polycyclic aromatic group; A non-fused polycyclic aliphatic group linked to each other; a non-fused polycyclic aromatic group in which the aromatic groups are linked to each other directly or by a cross-linking member.
  • the tetracarboxylic dianhydride represented by the general formula (a) is particularly preferably an aromatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride.
  • aromatic tetracarboxylic dianhydride represented by the general formula (a) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4 -Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene
  • Examples of the alicyclic tetracarboxylic dianhydride represented by the general formula (a) include cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7 -Ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentyl acetic acid dianhydride, bicyclo [2.2.1] heptane-2,3,5-tricarboxylic acid-6-acetic acid dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3
  • the tetracarboxylic dianhydride represented by the general formula (a) includes an aromatic ring such as a benzene ring, a part or all of the hydrogen atoms on the aromatic ring are a fluoro group, a methyl group, a methoxy group It may be substituted with a group, a trifluoromethyl group, a trifluoromethoxy group, or the like.
  • the tetracarboxylic dianhydride represented by the general formula (a) includes an aromatic ring such as a benzene ring, the ethynyl group, benzocyclobuten-4′-yl group, vinyl A group serving as a crosslinking point selected from a group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, an isopropenyl group, and the like may be included in the structure of the tetracarboxylic acid.
  • an aromatic ring such as a benzene ring, the ethynyl group, benzocyclobuten-4′-yl group, vinyl A group serving as a crosslinking point selected from a group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, an isopropenyl group, and the like.
  • the tetracarboxylic dianhydride represented by the general formula (a) has a main clavicle group having a crosslinking point such as a vinylene group, a vinylidene group, and an ethynylidene group within a range that does not impair molding processability. It is preferably incorporated in the case.
  • the tetracarboxylic acid component (A) may include hexacarboxylic dianhydrides and octacarboxylic dianhydrides in addition to the tetracarboxylic dianhydrides represented by the general formula (a). .
  • these anhydrides When these anhydrides are contained, a branched chain is introduced into the resulting polyimide. Only one kind of these anhydrides may be contained, or two or more kinds may be contained.
  • Diamine component (B) The diamine component (B) constituting the polyimide precursor includes diamines represented by the following general formulas (b-1) to (b-3).
  • the diamine component (B) may contain only one diamine represented by the following general formulas (b-1) to (b-3), or may contain two or more. Further, the diamine component (B) may contain a diamine (b-4) other than the diamines represented by the general formulas (b-1) to (b-3).
  • the cyclohexane skeleton of cyclohexadiamine represented by the general formula (b-1) has the following two geometric isomers (cis isomer / trans isomer).
  • the trans isomer is represented by the following general formula (Z-1)
  • the cis isomer is represented by the following general formula (Z-2).
  • the cis / trans ratio of the cyclohexane skeleton in the general formula (Z-1) is preferably 50/50 to 0/100, and more preferably 30/70 to 0/100.
  • the proportion of the trans isomer increases, the molecular weight of the polyimide precursor generally tends to increase. Therefore, the strength of the film is likely to increase.
  • the cis / trans ratio of the unit derived from cyclohexane contained in the polyimide precursor is measured by nuclear magnetic resonance spectroscopy.
  • the position of the aminomethyl group of norbornanediamine represented by the general formula (b-2) is not particularly limited.
  • the norbornanediamine represented by the general formula (b-2) may include structural isomers having different aminomethyl group positions, optical isomers including S and R isomers, and the like. These may be included in any ratio.
  • the 1,4-bismethylenecyclohexane skeleton (X) of 1,4-bis (aminomethyl) cyclohexane represented by the general formula (b-3) has two geometric isomers (cis isomer / trans isomer). is there.
  • the trans isomer is represented by the following general formula (X1)
  • the cis isomer is represented by the following general formula (X2).
  • the cis / trans ratio of the unit derived from 1,4-bis (aminomethyl) cyclohexane is preferably 40/60 to 0/100, and more preferably 20/80 to 0/100.
  • the glass transition temperature of the polyimide containing the diamine represented by the general formula (b-3) as a constituent component is controlled by the above cis / trans ratio, and when the ratio of the trans form (X1) increases, the glass transition temperature of the polyimide Will increase.
  • the cis / trans ratio of the unit derived from 1,4-bis (aminomethyl) cyclohexane contained in the polyimide precursor is measured by nuclear magnetic resonance spectroscopy.
  • the diamine component (B) may contain a diamine (b-4) represented by the following general formula other than the diamines represented by the above general formulas (b-1) to (b-3). .
  • R ′ is a divalent group having 4 to 51 carbon atoms.
  • R ′ represents an aliphatic group; a monocyclic aliphatic group (however, a 1,4-cyclohexylene group, a group represented by the following general formula (X), and a group represented by the following general formula (Y)): Excluded); condensed polycyclic aliphatic group; monocyclic aromatic group; condensed polycyclic aromatic group; non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are connected to each other directly or by a bridging member A non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member.
  • Examples of the diamine represented by the general formula (b-4) include a diamine having a benzene ring, a diamine having an aromatic substituent, a diamine having a spirobiindane ring, a siloxane diamine, an ethylene glycol diamine, and an alkylene diamine. , Alicyclic diamines and the like.
  • diamines having a benzene ring examples include ⁇ 1> Diamine having one benzene ring such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine; ⁇ 2> 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′- Diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminobenzophenone, 4,4′-
  • diamines with aromatic substituents examples include 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino -4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone and the like are included.
  • diamines having a spirobiindane ring examples include 6,6′-bis (3-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis ( 4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane and the like.
  • siloxane diamines examples include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, ⁇ , ⁇ -bis (3-aminopropyl) ) Polydimethylsiloxane, ⁇ , ⁇ -bis (3-aminobutyl) polydimethylsiloxane and the like.
  • Examples of ethylene glycol diamines include bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis [(2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, , 2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-amino Propyl) ether, triethylene glycol bis (3-aminopropyl) ether, and the like.
  • alkylene diamines examples include ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane. 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like are included.
  • alicyclic diamines examples include cyclobutanediamine, cyclohexanediamine, di (aminomethyl) cyclohexane [bis (aminomethyl) cyclohexane excluding 1,4-bis (aminomethyl) cyclohexane], diaminobicycloheptane, diaminomethylbicyclo Heptane (including norbornanediamines such as norbornanediamine), diaminooxybicycloheptane, diaminomethyloxybicycloheptane (including oxanorbornanediamine), isophoronediamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis (aminocyclohexane) Xyl) methane [or methylenebis (cyclohexylamine)], bis (aminocyclohexyl) isopropylidene and the like.
  • polyimide precursor contained in the polyimide precursor-containing solution is not particularly limited as long as the tetracarboxylic acid component (A) and the diamine component (B) described above are reacted,
  • the polyimide precursor is a polyamic acid block (represented by the following general formula (G)) of a tetracarboxylic dianhydride represented by the general formula (a) and a diamine represented by the general formula (b-1).
  • R 6 and R 8 each independently represents a tetravalent group having 4 to 27 carbon atoms.
  • R 6 and R 8 are each independently an aliphatic group; a monocyclic aliphatic group; a condensed polycyclic aliphatic group; a monocyclic aromatic group; or a condensed polycyclic aromatic group; A non-condensed polycyclic aliphatic group directly or linked to each other by a bridging member; a non-fused polycyclic aromatic group whose aromatic groups are linked to each other directly or by a bridging member. Specifically, it is the same as R 1 in the tetracarboxylic dianhydride represented by the general formula (a).
  • R 7 represents a divalent group having 4 to 51 carbon atoms.
  • R 7 represents an aliphatic group; a monocyclic aliphatic group (excluding a 1,4-cyclohexylene group); a condensed polycyclic aliphatic group; a monocyclic aromatic group or a condensed polycyclic aromatic group;
  • a non-condensed polycyclic aliphatic group in which the cycloaliphatic groups are linked to each other directly or via a bridging member; may be a non-fused polycyclic aromatic group in which the aromatic groups are linked to each other directly or by a bridging member .
  • R 7 in the general formula (H) is particularly preferably a norbornane (a group represented by the above general formula (Y)). That is, the polyimide block represented by the general formula (H) is preferably a polyimide block containing a diamine represented by the general formula (b-2).
  • M and n in Formula (G) and Formula (H) indicate the number of repeating structural units in each block.
  • the average value of m and the average value of n are each independently preferably 2 to 1000, and more preferably 5 to 500.
  • the ratio of the repeating number m of the repeating structural unit represented by the formula (G) is a certain value or more, the thermal expansion coefficient of the obtained polyimide film becomes small. Moreover, the visible light transmittance
  • cyclohexanediamine is generally expensive, reducing the ratio of the number m of repeating structural units represented by the formula (G) can reduce the cost.
  • the solvent contained in the polyimide precursor-containing solution is not particularly limited as long as it is a solvent that can dissolve the tetracarboxylic acid component (A) and the diamine component (B).
  • it may be an aprotic polar solvent or a water-soluble alcohol solvent.
  • aprotic polar solvents examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazo Lidinone, etc .; ether compounds such as 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monoethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethylene Toxi-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropy
  • water-soluble alcohol solvents examples include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol. 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 1,2,6-hexane Triol, diacetone alcohol and the like are included.
  • the polyimide precursor-containing solution may contain only one kind of these solvents, or may contain two or more kinds.
  • the solvent preferably contains N, N-dimethylacetamide, N-methyl-2-pyrrolidone, or a mixture thereof.
  • the release agent may be contained in the polyimide precursor containing solution.
  • the release agent contained in the polyimide precursor-containing solution is not particularly limited as long as the release property between the support substrate and the transparent polyimide layer can be improved, and may be a known internal release agent.
  • the internal release agent include aliphatic alcohols, fatty acid esters, triglycerides, fluorine surfactants, higher fatty acid metal salts, and phosphate ester release agents. From the viewpoint that the transparency of the transparent polyimide layer to be obtained is hardly hindered, it is preferably a phosphate ester release agent.
  • the phosphoric ester release agent include compounds described in JP-A No. 2000-256377.
  • the amount of the release agent contained in the polyimide precursor-containing solution is preferably 0.01 to 0.38 parts by weight, more preferably 100 parts by weight of the polyimide precursor contained in the polyimide precursor-containing solution.
  • the amount is 0.02 to 0.30 parts by mass, more preferably 0.04 to 0.20 parts by mass.
  • the amount of the release agent is less than 0.01 parts by mass, the peel strength when the transparent polyimide layer is peeled off from the support substrate is increased.
  • the amount of the release agent exceeds 0.38 parts by mass, it becomes difficult to apply the polyimide precursor-containing solution on the support substrate.
  • the polyimide precursor-containing solution may contain various additives as long as the transparency and heat resistance of the obtained transparent polyimide layer are not impaired.
  • various additives include antioxidants, heat stabilizers, antistatic agents, flame retardants, and ultraviolet absorbers.
  • the polyimide precursor-containing solution is obtained by reacting the aforementioned tetracarboxylic acid component (A) and the aforementioned diamine component (B) in the aforementioned solvent.
  • y / x is preferably 0.9 to 1.1, 0.95 Is more preferably from 1.07 to 1.05, further preferably from 0.97 to 1.03, particularly preferably from 0.99 to 1.01.
  • the polymerization reaction procedure is not particularly limited. For example, first, a container equipped with a stirrer and a nitrogen introduction tube is prepared. A solvent described later is put into a nitrogen-substituted container, diamine is added so that the solid content concentration of the obtained polyimide precursor is 50% by mass or less, and the temperature is adjusted, followed by stirring and dissolution. To this solution, the tetracarboxylic acid component (A) is added so that the molar ratio is 1 with respect to the diamine component (B), the temperature is adjusted, and the mixture is stirred for about 1 to 50 hours, whereby the polyimide precursor is obtained. The polyimide precursor containing solution to contain can be obtained.
  • a polyamic acid imide may be generated by adding an acid anhydride-terminated polyimide solution to an amine-terminated polyamic acid solution and stirring.
  • the diamine unit of the polyamic acid preferably contains a cyclohexane-containing diamine (the diamine represented by the general formula (b-1) or (b-3) described above); the polyimide diamine unit contains a cyclohexane-containing diamine. It is preferable that a diamine other than the above (a diamine represented by the aforementioned general formula (b-2) or (b-4)) is included.
  • polyimide containing a cyclohexane in the structure (diamine represented by (b-1) or (b-3)) may be difficult to dissolve in a solvent.
  • Polyamic acid is produced by the method described above.
  • a mold release agent is added suitably as needed.
  • the total light transmittance of the transparent polyimide layer in the transparent polyimide laminate obtained by the above-described method is 80% or more, more preferably 83% or more, and further preferably 85% or more. If the total light transmittance is 80% or more, the transparent polyimide layer can be applied to applications requiring transparency.
  • the total light transmittance of the transparent polyimide layer is adjusted by the kind of polyimide, the oxygen concentration of the atmosphere in the above-described step b), the pressure, and the like. In particular, by reducing the oxygen concentration of the atmosphere in the temperature range exceeding 200 ° C.
  • step b) or lowering the pressure of the atmosphere, the oxidation of the polyimide is suppressed and the total light transmittance of the transparent polyimide layer is increased.
  • the total light transmittance is measured with a light source D65 in accordance with JIS-K7105 after peeling the transparent polyimide layer from the support substrate.
  • the in-plane retardation of the transparent polyimide layer in the transparent polyimide laminate is 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less. If the in-plane retardation of the transparent polyimide layer is 10 nm or less, the transparent polyimide layer can be applied to a panel substrate of a flexible display device. If imidization partially proceeds after the completion of the above-mentioned step b) or if the solvent is volatilized, the in-plane retardation tends to increase.
  • the in-plane retardation is a value measured with a photoelastic constant measuring device with light at 25 ° C. and a wavelength of 550 nm.
  • the transparent polyimide layer is peeled from the support substrate, the refractive index of the transparent polyimide layer is measured with a photoelastic constant measuring device, the direction in which the refractive index is maximum is the X axis, and the direction perpendicular to the X axis Is the Y axis.
  • the refractive index in the X-axis direction is nx
  • the refractive index in the Y-axis direction is ny
  • the thickness of the transparent polyimide layer is d
  • the value represented by (nx ⁇ ny) ⁇ d is the in-plane retardation.
  • the glass transition temperature (Tg) of the transparent polyimide layer in the transparent polyimide laminate is 260 ° C. or higher, preferably 270 ° C. or higher, more preferably 300 ° C. or higher.
  • Tg glass transition temperature
  • the transparent polyimide layer can be applied to applications requiring high heat resistance.
  • the process temperature for forming an electronic element is generally 250 ° C., and the transparent polyimide layer obtained by the present invention can be applied to a panel substrate of an apparatus including such an electronic element.
  • the glass transition temperature of the transparent polyimide layer is adjusted by, for example, the equivalent of the imide group contained in the polyimide, the structure of the diamine component or tetracarboxylic dianhydride component constituting the polyimide, and the like.
  • the glass transition temperature is measured with a thermomechanical analyzer (TMA).
  • the haze of the transparent polyimide layer in the transparent polyimide laminate is 5% or less, preferably 3% or less, and more preferably 1% or less.
  • the transparent polyimide layer can be applied to various optical films.
  • the haze of the transparent polyimide layer is adjusted by the heating conditions of the polyimide precursor-containing solution, the crystallinity of the polyimide, the surface roughness of the support substrate, and the like.
  • the absolute value of the b value represented by the L * a * b color system of the transparent polyimide layer is 5 or less, preferably 3 or less.
  • the b value is preferably a positive value (0 or more).
  • the L * a * b color system is standardized in JIS Z 8729.
  • the transparent polyimide layer is yellowish, and when the b value is a negative value, the transparent polyimide layer is bluish.
  • a general polyimide film has a large b value and is often yellow or brown.
  • the transparent polyimide layer in the transparent polyimide laminate of the present invention has an absolute value of b value of 5 or less and is less colored. Therefore, the polyimide layer can be applied to various display substrates.
  • the thickness of the transparent polyimide layer in the transparent polyimide laminate is not particularly limited, but is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m. When the transparent polyimide layer has such a thickness, it can be used as a substrate for various flexible devices.
  • the present invention has a glass transition temperature of 260 ° C. or higher, a total light transmittance of 80% or higher, a haze of 5% or lower, an absolute value of b value in the L * a * b color system of 5 or lower, and a surface.
  • a polyimide film having an internal retardation of 10 nm or less is also provided. It is preferable that the said polyimide film consists of a transparent polyimide layer obtained with the manufacturing method of the above-mentioned transparent polyimide laminated body. Furthermore, it is preferable that the physical property of the said polyimide film is the same range as the above-mentioned polyimide layer.
  • the transparent polyimide film obtained by peeling the transparent polyimide layer of the above-mentioned transparent polyimide laminated body from a support base material is applicable to the board
  • the transparent polyimide film has a high total light transmittance and a very small in-plane retardation, it is particularly suitable for a flexible display substrate.
  • the flexible display include a touch panel, a liquid crystal display, and an organic EL display.
  • a touch panel is generally a panel body composed of (i) a transparent substrate having a transparent electrode (detection electrode layer), (ii) an adhesive layer, and (iii) a transparent substrate having a transparent electrode (drive electrode layer). .
  • the above-mentioned transparent polyimide film can be applied to both the transparent substrate on the detection electrode layer side and the transparent substrate on the drive electrode layer side.
  • the liquid crystal cell of the liquid crystal display device is usually a laminate in which (i) a first transparent plate, (ii) a liquid crystal material sandwiched between transparent electrodes, and (iii) a second transparent plate are laminated in this order.
  • the aforementioned transparent polyimide film can be applied to both the first transparent plate and the second transparent plate.
  • the transparent polyimide film described above can also be applied to a substrate for a color filter in a liquid crystal display device.
  • An organic EL panel is usually a panel in which a transparent substrate, an anode transparent electrode layer, an organic EL layer, a cathode reflective electrode layer, and a counter substrate are laminated in this order.
  • the transparent polyimide film described above can be applied to both the transparent substrate and the counter substrate.
  • the transparent polyimide layer (transparent polyimide film) of the transparent polyimide laminate described above is easily peeled off from the support substrate. Therefore, when obtaining a flexible display, the transparent polyimide layer may be peeled off, and then an element may be formed on the transparent polyimide layer. After forming the element on the transparent polyimide layer, the transparent polyimide layer is supported on the support substrate. You may peel from.
  • an antistatic agent is added to a polyimide precursor-containing solution, (b) an antistatic agent is coated on a support substrate, (c) a polyimide precursor-containing solution coating apparatus or a transparent polyimide layer
  • a static eliminating member for example, a neutralizing bar, a neutralizing yarn, an ion blowing static eliminating device, etc.
  • a method for forming an element is not particularly limited, and may be a known method.
  • the 1st method peels transparent polyimide film (transparent polyimide layer) 1 'from the support base material 11 in the transparent polyimide laminated body 12, as shown by the schematic sectional drawing of FIG. After that (FIG. 2A), the element 13 is formed on the transparent polyimide film 1 ′ (FIG. 2B).
  • the element 13 can be formed on the transparent polyimide film 1 ′ after the peeled transparent polyimide film 1 ′ is bonded to another substrate (not shown).
  • the second method is to form the element 13 on the transparent polyimide layer 1 ′ laminated with the support base 11 (FIG. 3 ( a)), a transparent polyimide film (transparent polyimide layer) 1 ′ is peeled from the support substrate 11 (FIG. 3B), and a transparent polyimide film 1 ′ having an element 13 formed thereon is obtained (FIG. 3). (C)).
  • the stress applied to the transparent polyimide layer 1 ′ when the element 13 is formed is easily absorbed by the support base material 11. Therefore, it is difficult for the transparent polyimide layer 1 ′ to tear or break when the element 13 is formed.
  • the third method is performed after the supporting base material 11 side of the transparent polyimide laminate 12 is bonded to another substrate 14 (FIG. 4 ( a)), various elements 13 are formed on the transparent polyimide layer 1 ′ (FIG. 4B), and the transparent polyimide film (transparent polyimide layer) 1 ′ is peeled from the support substrate 11 (FIG. 4C). ), And a method of obtaining a polyimide film 1 ′ on which the element 13 is formed (FIG. 4D). In the third method, since the other substrate 14 is bonded to the transparent polyimide laminate 12, the transparent polyimide laminate 12 does not bend when the element 13 is manufactured.
  • the element 13 can be formed on the transparent polyimide layer 1 ′ by various methods. Also in the third method, the stress applied to the transparent polyimide layer 1 ′ during the formation of the element 13 is easily absorbed by the support base material 11. Therefore, it is difficult for the transparent polyimide layer 1 ′ to tear or break when the element 13 is formed.
  • the other substrate 14 to be bonded to the transparent polyimide laminate 12 is not particularly limited as long as it is a rigid substrate, and may be a glass substrate, a metal substrate, a ceramic substrate, a resin substrate, or the like.
  • the bonding method between the support base 11 of the transparent polyimide laminate 12 and the other substrate 14 is not particularly limited, and may be a method of bonding with an adhesive or the like, for example.
  • the method for producing a polyimide laminate described above can also be applied to a method for producing a resin laminate having a support base and various resin layers. Specifically, it is set as the manufacturing method of a resin laminated body which has the process of (a) apply
  • various resins include polyimide resins (polyimide precursors) other than those described above, aramid resins, polyether ether ketone resins, and polyether sulfone resins.
  • the transparent polyimide laminates produced in the examples and comparative examples were cut into a length of 50 mm and a width of 3.5 mm.
  • the peel strength of this transparent polyimide laminate was measured according to the method specified in JIS C-6471. Specifically, the edge of the short side of the transparent polyimide laminate was gripped, peeled from the support substrate at a peeling angle of 90 °, and a peeling speed of 50 mm / min, and the stress at the time of peeling was measured. The stress was measured with a tensile tester EZ-S manufactured by Shimadzu Corporation and an adhesive tape peeling tester.
  • the transparent polyimide layer was peeled off from the transparent polyimide laminates prepared in Examples and Comparative Examples, and the imidization rate of the transparent polyimide layer was calculated as follows.
  • the IR absorption spectrum was measured by attaching a multiple reflection infrared spectrum measuring device (ATR PR0410-M manufactured by JASCO Corporation) to an FT-IR spectrometer (FT / IR 300E manufactured by JASCO Corporation). .
  • IR absorption spectrum was measured, respectively.
  • the absorption peak height of 1370 cm ⁇ 1 (CN stretching vibration of the imide ring) with respect to the absorption peak height of 1500 cm ⁇ 1 (peak (reference) due to C C stretching vibration of the benzene ring).
  • the ratio A was calculated.
  • a transparent polyimide layer was prepared in the same manner as in each Example and Comparative Example, and this was heated at 270 ° C. for 2 hours or longer to completely imidize.
  • the transparent polyimide layer was peeled from the transparent polyimide laminates produced in Examples and Comparative Examples, and the residual amount of solvent in the transparent polyimide layer was measured.
  • the measurement was carried out using an electric furnace type pyrolysis furnace (Shimadzu PYR-2A (pyrolysis temperature 320 ° C.)) and a gas chromatograph / mass spectrometer (Shimadzu GC-8A (Column Uniport HP 80/100 KG-02)). And the amount of solvent contained in the film was specified.
  • the injector and detector temperatures of the apparatus were 200 ° C., and the column temperature was 170 ° C.
  • the transparent polyimide layer was peeled from the transparent polyimide laminates prepared in Examples and Comparative Examples, and the total light transmittance of the transparent polyimide layer was measured. Specifically, in accordance with JIS-K-7105, measurement was performed with a light source D65 using a Nippon Denshoku Haze Meter NDH2000.
  • the transparent polyimide layer was peeled from the transparent polyimide laminates produced in Examples and Comparative Examples, and the haze of the transparent polyimide layer was measured. Specifically, in accordance with JIS-K-7105, measurement was performed with a light source D65 using a Nippon Denshoku Haze Meter NDH2000.
  • the transparent polyimide layer was peeled from the transparent polyimide laminates produced in the examples and comparative examples, and the b value of the transparent polyimide layer was measured.
  • a color difference meter (measuring head: CM-2500d, manufactured by Konica Minolta Co., Ltd.) was used, and the b value of the transparent polyimide layer was measured three times on a calibration white plate with a C light source, 2 °, field of view, and SCI mode. Measured.
  • the b value was an average value of three measurement values.
  • the transparent polyimide layer was peeled from the transparent polyimide laminate produced in the examples and comparative examples.
  • the in-plane retardation of the transparent polyimide layer was measured by the X, Y mode of a photoelastic constant measuring device PEL-3A-102C manufactured by UNIOPT.
  • the measurement temperature was 25 ° C.
  • the measurement wavelength was 550 nm.
  • the refractive index of the polyimide film is measured with a photoelastic constant measuring device, the direction in which the refractive index is maximum is the X axis, the direction perpendicular to the X axis is the Y axis, and the refractive index nx in the X axis direction.
  • a refractive index ny in the Y-axis direction was defined as the in-plane retardation.
  • Ten-point average roughness of supporting substrate The ten-point average roughness of the supporting substrates used in Examples and Comparative Examples was measured according to JIS B0601. At this time, with a cut-off value of 0.25 mm and a measurement length of 2.5 mm, the ten-point average roughness in the width direction of the support substrate was measured with a surface roughness / contour shape measuring machine (Surfcom 1400D manufactured by Tokyo Seimitsu). .
  • a cooling tube and a Dean-Stark type concentrator were attached to the separable flask, 80.0 g of xylene was added to the reaction solution, and dehydration thermal imidization reaction was performed at 180 ° C. for 4 hours while stirring. After the reaction, xylene was distilled off to obtain an imide oligomer solution having an acid anhydride structure derived from BPDA at the end.
  • Example 1 The polyimide precursor-containing solution prepared in Synthesis Example 1 was applied with a doctor blade onto a Ube Industries polyimide film (UPILEX 50S (50 ⁇ m)) fixed to a glass substrate with Kapton tape. And the sample which consists of a glass substrate, a support base material, and a polyimide precursor film was put into inert oven. Thereafter, the oxygen concentration in the inert oven is controlled to 0.0%, the temperature is increased from 30 ° C. to 270 ° C. over 120 minutes (temperature increase rate: 2 ° C./min), and further maintained at 270 ° C. for 2 hours. A transparent polyimide laminate was produced on the substrate. The thickness of the obtained transparent polyimide layer was 30 ⁇ m.
  • Ube Industries polyimide film UPILEX 50S (50 ⁇ m)
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.039 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 260 ° C.
  • the total light transmittance is 87%
  • the in-plane retardation (R0) is 0.8 nm
  • the imidization rate is 98%
  • the residual solvent amount is It was 0.2% by mass.
  • Example 2 A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 1 except that the oxygen concentration in the inert oven was changed to 5.0%.
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.039 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 261 ° C., the total light transmittance is 87%, the in-plane retardation (R0) is 0.8 nm, the imidization rate is 98%, and the residual solvent amount is It was 0.2% by mass.
  • Example 3 A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 1 except that the heating rate was changed to 10 ° C./min.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 260 ° C.
  • the total light transmittance is 87%
  • the in-plane retardation (R0) is 0.7 nm
  • the imidization rate is 95%
  • the residual solvent amount is It was 0.5 mass%.
  • Example 4 A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 3 except that the maximum temperature of the inert oven was changed to 280 ° C. and the rate of temperature increase was 2 ° C./min.
  • the transparent polyimide film after peeling has a glass transition temperature (Tg) of 261 ° C., a total light transmittance of 86%, an in-plane retardation (R0) of 0.7 nm, an imidization rate of 100%, and a residual solvent detected. Was not.
  • Example 5 The polyimide precursor-containing solution prepared in Synthesis Example 1 was applied with a doctor blade onto a Ube Industries polyimide film (UPILEX50S) fixed to a glass substrate with Kapton tape. And the sample which consists of a glass substrate, a support base material, and a polyimide precursor film was put into inert oven. Thereafter, the oxygen concentration in the inert oven was controlled to 20%, the temperature was raised from 30 ° C. to 180 ° C. over 75 minutes (temperature increase rate 2 ° C./min), and further maintained at 180 ° C. for 2 hours. Thereafter, the sample was transferred to a vacuum oven, and the temperature was increased after the vacuum was reduced to 1 kPa or less with full vacuum.
  • Ube Industries polyimide film UPILEX50S
  • the vacuum oven was heated from 30 ° C. to 270 ° C. over 60 minutes (temperature increase rate: 4 ° C./min), and further maintained at 270 ° C. for 1 hour to produce a transparent polyimide laminate on the glass substrate.
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.031 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 260 ° C.
  • the total light transmittance is 86%
  • the in-plane retardation (R0) is 0.5 nm
  • the imidization rate is 96%
  • the residual solvent amount is It was 0.7 mass%.
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.029 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 290 ° C.
  • the total light transmittance is 88%
  • the in-plane retardation (R0) is 0.3 nm
  • the imidization rate is 98%
  • the residual solvent amount is It was 0.6 mass%.
  • Example 7 A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 1 except that the polyimide precursor-containing solution to be used was changed to that prepared in Synthesis Example 3 and the temperature increase rate was 2 ° C./min.
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.041 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 266 ° C.
  • the total light transmittance is 88%
  • the in-plane retardation (R0) is 0.6 nm
  • the imidization rate is 96%
  • the residual solvent amount is It was 0.3% by mass.
  • the polyimide precursor-containing solution prepared in Synthesis Example 1 was coated on a Tokai aluminum aluminum foil (50 ⁇ m) fixed to a glass substrate with Kapton tape with a doctor blade. And the sample which consists of a glass substrate, a support base material, and a polyimide precursor film was put into inert oven. Thereafter, the oxygen concentration in the inert oven is controlled to 0.0%, the temperature is increased from 30 ° C. to 270 ° C. over 120 minutes (temperature increase rate: 2 ° C./min), and further maintained at 270 ° C. for 2 hours. A transparent polyimide laminate was produced on the substrate.
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.19 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 261 ° C.
  • the total light transmittance is 85%
  • the in-plane retardation (R0) is 1.4 nm
  • the imidization rate is 99%
  • the residual solvent amount is It was 0.1 mass%.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 260 ° C.
  • the total light transmittance is 85%
  • the in-plane retardation (R0) is 1.1 nm
  • the imidization rate is 99%
  • the residual solvent amount is It was 0.1 mass%.
  • Example 8 The polyimide precursor-containing solution prepared in Synthesis Example 1 was continuously and continuously cast onto a polyimide film (UPILEX 50S (50 ⁇ m)) manufactured by Ube Industries using a die coater, and the oxygen concentration was adjusted to 0.0%. Using a controlled drying furnace, the temperature was raised stepwise (corresponding to a heating rate of 5 ° C./min) and heated to a maximum temperature of 270 ° C. to produce a transparent polyimide laminate. The peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.039 kN / m.
  • UPILEX 50S 50 ⁇ m
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 261 ° C.
  • the total light transmittance is 87%
  • the in-plane retardation (R0) is 2.0 nm
  • the imidization rate is 97%
  • the residual solvent amount is It was 0.8 mass%.
  • the thickness of the transparent polyimide layer of the obtained transparent polyimide laminate was 30 ⁇ m.
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.030 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 286 ° C., the total light transmittance is 85%, the haze is 1.0%, the b value is 1.8, and the in-plane retardation (R0) is 0.9 nm.
  • the imidation ratio was 98%, and the solvent residual amount was 0.5% by mass.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling was not detected, the total light transmittance was 78%, the in-plane retardation (R0) was 0.9 nm, the imidization rate was 95%, and the solvent remaining amount was 0.9 mass%.
  • Example 2 A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 1 except that the oxygen concentration in the inert oven was changed to 10.0%.
  • the peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.031 kN / m.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 259 ° C., the total light transmittance is 79%, the in-plane retardation (R0) is 0.8 nm, the imidization rate is 97%, and the residual solvent amount is It was 0.5 mass%.
  • Example 3 A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 1 except that the maximum temperature of the inert oven was changed to 230 ° C.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 250 ° C.
  • the total light transmittance is 90%
  • the in-plane retardation (R0) is 0.8 nm
  • the imidization rate is 78%
  • the residual solvent amount is It was 3.0 mass%.
  • Example 4 A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 1 except that the supporting substrate used was changed to a copper foil (NA-DFF (12 ⁇ m)) manufactured by Mitsui Metal Mining. Although an attempt was made to peel off the transparent polyimide layer from the copper foil (support base material) of the transparent polyimide laminate removed from the glass substrate, it could not be removed.
  • NA-DFF copper foil
  • the glass substrate / transparent polyimide layer was immersed in distilled water to peel the transparent polyimide film from the glass substrate.
  • the glass transition temperature (Tg) of the transparent polyimide film after peeling is 260 ° C.
  • the total light transmittance is 87%
  • the in-plane retardation (R0) is 0.8 nm
  • the imidization rate is 98%
  • the residual solvent amount is It was 0.1 mass%.
  • the transparent polyimide film after peeling was fixed to the stainless steel metal frame with Kapton tape all around. This was put into an inert oven, the oxygen concentration in the inert oven was controlled to 0.0%, and the temperature was increased from 30 ° C. to 250 ° C. over 110 minutes (temperature increase rate 2 ° C./min). And it hold
  • the glass transition temperature (Tg) of the obtained transparent polyimide film was 258 ° C., the total light transmittance was 87%, the haze was 3.7%, the b value was 0.9, the in-plane retardation (R0) was 80 nm, and the imide The conversion rate was 88%, and the residual solvent amount was 1.5% by mass.
  • the peeled film was fixed to the stainless steel metal frame with Kapton tape. This is put into an inert oven, the oxygen concentration in the inert oven is controlled to 0.0%, the temperature is raised from 30 ° C. to 270 ° C. over 120 minutes (temperature rising rate 2 ° C./min), and further 2 at 270 ° C. Holding for a time, a transparent polyimide film having a thickness of 30 ⁇ m was obtained.
  • the resulting transparent polyimide film had a glass transition temperature (Tg) of 260 ° C., a total light transmittance of 88%, a haze of 1.5%, a b value of 0.8, an in-plane retardation (R0) of 12 nm, and an imide.
  • Tg glass transition temperature
  • R0 in-plane retardation
  • Example 1 when the polyimide precursor was heated at a temperature equal to or higher than the glass transition temperature of the resulting transparent polyimide layer (Examples 1 to 9, Reference Examples 1 to 3, Comparative Examples 2 and 6, and Comparative Example) In Example 8), the residual solvent amount was 1.0% by mass or less, and the imidization ratio was 95% or more. On the other hand, when heated below the glass transition temperature of the transparent polyimide layer obtained (Comparative Example 3 and Comparative Example 7), the residual solvent amount is 3.0% by mass, and the imidization rate is less than 90%. The drying of the solvent and the imidization of the polyimide precursor were insufficient.
  • the peel strength when peeling the transparent polyimide layer from the support substrate is 0.041 kN / m or less, and the peelability of the transparent polyimide layer was good.
  • the support substrate was an aluminum substrate, the peel strength when peeling the transparent polyimide layer from the support substrate was relatively high at 0.19 kN / m (Reference Example 1).
  • the peel strength was greatly reduced when a release agent was included in the polyimide precursor-containing solution (Reference Example 2).
  • the supporting base material is copper foil, and the release agent is not included in the polyimide precursor-containing solution (Comparative Example 4)
  • the peel strength between the supporting base material and the transparent polyimide layer is high, and these can be peeled off. There wasn't.
  • the support base material was a glass substrate (Comparative Example 6)
  • the peel strength between the support base material and the transparent polyimide layer was high, and the transparent polyimide layer could not be peeled unless immersed in water.
  • the supporting base material is an aluminum substrate, a SUS plate, or the like
  • the ten-point average roughness (Rz) of the surface of the supporting base material is rough, and the haze of the transparent polyimide layer formed on the supporting base material is increased. It was easy (Reference Examples 1 to 3).
  • the transparent polyimide film obtained from the transparent polyimide laminate of the present invention has a high total light transmittance and a small in-plane retardation. Therefore, the present invention can be applied to various flexible display panel substrates such as a touch panel substrate, a color filter substrate, a liquid crystal cell substrate, and an organic EL display substrate.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne le problème de la fourniture d'un stratifié de polyimide transparent comprenant une couche de polyimide transparent qui présente un coefficient de transmissivité de lumière élevé et une petite différence de phase dans le plan, et qui peut être facilement séparé d'un substrat de support. Afin de résoudre le problème précité, l'invention concerne un procédé de fabrication de stratifié de polyimide transparent composé d'un substrat de support et d'une couche de polyimide transparent stratifiée sur le substrat de support, qui comprend: a) une étape de revêtement du substrat de support par une solution contenant un précurseur de polyimide qui contient un solvant et un précurseur de polyimide obtenu par réaction d'un composant d'acide tetracarboxylique et d'un composant de diamine ; et b) une étape de chauffage d'une couche mince de précurseur de polyimide formée à partir du revêtement par la solution contenant le précurseur de polyimide à au moins la température de transition vitreuse de la couche de polyimide transparent. Ladite couche de polyimide transparent présente une température de transition vitreuse de 260°C ou plus, un coefficient de transmissivité de lumière total de 80% ou plus, un trouble de 5% ou moins, une valeur absolue pour la valeur b d'un système de couleur L*a*b de 5 ou moins, et une différence de phase dans le plan de 10 nm ou moins. La force de détachement lorsque la couche de polyimide transparent est séparée du substrat de support est comprise entre 0,005 et 0,20 kN/m.
PCT/JP2013/005438 2012-09-14 2013-09-13 Stratifié de polyimide transparent et son procédé de fabrication WO2014041816A1 (fr)

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JPWO2016043180A1 (ja) * 2014-09-19 2017-07-06 ユニチカ株式会社 積層体およびフレキシブルデバイスの製造方法
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JP2021119243A (ja) * 2015-02-10 2021-08-12 日産化学株式会社 タッチパネルセンサーの製造方法
JP7131651B2 (ja) 2015-02-10 2022-09-06 日産化学株式会社 タッチパネルセンサーの製造方法
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