WO2014041816A1 - Transparent polyimide laminate and manufacturing method therefor - Google Patents
Transparent polyimide laminate and manufacturing method therefor Download PDFInfo
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- 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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- transparent polyimide
- transparent
- group
- polyimide
- film
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- 0 NC1CCC(*C=N)CC1 Chemical compound NC1CCC(*C=N)CC1 0.000 description 1
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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
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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
- B32B27/06—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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Abstract
Description
[3]前記ポリイミド前駆体含有溶液に、離型剤がさらに含まれる、[1]または[2]に記載のポリイミド積層体の製造方法。
[4]前記工程b)の200℃を超える温度領域では、雰囲気の酸素濃度を5体積%以下とする、[1]~[3]のいずれかに記載の透明ポリイミド積層体の製造方法。
[5]前記工程b)の200℃を超える温度領域では、雰囲気を減圧する、[1]~[3]のいずれかに記載の透明ポリイミド積層体の製造方法。
[6]前記工程b)は、150℃以下から200℃超まで昇温しながら前記ポリイミド前駆体フィルムを加熱する工程であり、前記工程b)における150~200℃の温度領域の平均昇温速度を0.25~50℃/分とする、[1]~[5]のいずれかに記載の透明ポリイミド積層体の製造方法。 [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).
[6] 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 method for producing a transparent polyimide laminate according to any one of [1] to [5], wherein is set to 0.25 to 50 ° C./min.
脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、もしくは縮合多環式芳香族基を示すか、環式脂肪族基が直接もしくは架橋員により相互に連結された非縮合多環式脂肪族基を示すか、または芳香族基が直接もしくは架橋員により相互に連結された非縮合多環式芳香族基を示す)
脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、もしくは縮合多環式芳香族基を示すか、環式脂肪族基が直接もしくは架橋員により相互に連結された非縮合多環式脂肪族基を示すか、または芳香族基が直接もしくは架橋員により相互に連結された非縮合多環式芳香族基を示す) [8] The polyimide precursor has a repeating unit represented by the following general formula (I), and the 1,4-bismethylenecyclohexane skeleton (X) in the general formula (I) is represented by the formula (X1). And a cis isomer represented by the formula (X2), the content ratio of the trans isomer to the cis isomer (trans isomer + cis isomer = 100%) is 60% ≦ trans isomer ≦ 100%, The method for producing a transparent polyimide laminate according to [7], wherein 0% ≦ cis body ≦ 40%.
一般式(H)において、R7は、炭素数4~51の2価の基であり、かつ脂肪族基、単環式脂肪族基(但し、1,4-シクロヘキシレン基を除く)、縮合多環式脂肪族基、単環式芳香族基もしくは縮合多環式芳香族基であるか、環式脂肪族基が直接もしくは架橋員により相互に連結された非縮合多環式脂肪族基であるか、または芳香族基が直接もしくは架橋員により相互に連結された非縮合多環式芳香族基である) [9] 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) The method for producing a transparent polyimide laminate according to any one of [1] to [6], which is a block polyamic acid imide having:
In the 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 groups are connected to each other directly or by a bridging member)
[11]前記[1]~[9]のいずれかに記載の製造方法から得られる、透明ポリイミド積層体。
[12]前記[11]記載の透明ポリイミド積層体の支持基材から透明ポリイミド層を剥離して得られる、光学フィルム。 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].
[12] An optical film obtained by peeling a transparent polyimide layer from a support substrate of the transparent polyimide laminate according to [11].
[13]前記[11]記載の透明ポリイミド積層体の支持基材から透明ポリイミド層を剥離し、透明ポリイミドフィルムを得る工程を含む、透明ポリイミドフィルムの製造方法。
[14]前記[11]記載の透明ポリイミド積層体の前記透明ポリイミド層上に素子を形成する工程と、前記素子を形成後の前記透明ポリイミド層を、前記支持基材から剥離する工程とを有する、フレキシブルデバイスの製造方法。
[15]前記[11]記載の製造方法で得られる透明ポリイミドフィルム上に素子を形成する工程を有する、フレキシブルデバイスの製造方法。
[16]前記[14]または[15]に記載のフレキシブルデバイスの製造方法により得られるタッチパネルディスプレイ。
[17]前記[14]または[15]に記載のフレキシブルデバイスの製造方法により得られる液晶ディスプレイ。
[18]前記[14]または[15]に記載のフレキシブルデバイスの製造方法により得られる有機ELディスプレイ。 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.
[13] 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.
[14] A step of forming an element on the transparent polyimide layer of the transparent polyimide laminate according to [11], and a step of peeling the transparent polyimide layer after forming the element from the support substrate. A manufacturing method of a flexible device.
[15] 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].
[16] A touch panel display obtained by the method for producing a flexible device according to [14] or [15].
[17] A liquid crystal display obtained by the method for producing a flexible device according to [14] or [15].
[18] An organic EL display obtained by the method for producing a flexible device according to [14] or [15].
本発明の製造方法では、支持基材と、透明ポリイミド層とを含む透明ポリイミド積層体であって、支持基材から透明ポリイミド層を剥離する際のピール強度が0.005~0.20kN/mであり、好ましくは0.01~0.15kN/m、さらに好ましくは0.05~0.10kN/mである透明ポリイミド積層体を製造する。ピール強度は、JIS C-6471(剥離角度90°)に準拠して測定される値である。 A. The manufacturing method of a transparent polyimide laminated body In the manufacturing method of this invention, it 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 °).
a)テトラカルボン酸成分及びジアミン成分を反応させてなるポリイミド前駆体と溶剤とを含むポリイミド前駆体含有溶液を、支持基材上に塗布する工程
b)前記ポリイミド前駆体含有溶液の塗膜からなるポリイミド前駆体フィルムを、透明ポリイミド層のガラス転移温度以上で加熱する工程 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
テトラカルボン酸成分及びジアミン成分を反応させてなるポリイミド前駆体と溶剤とを含むポリイミド前駆体含有溶液を準備する。ポリイミド前駆体含有溶液に含まれるポリイミド前駆体の種類は、特に制限されないが、得られる透明ポリイミド層の全光線透過率を高めるとの観点から、ポリイミド前駆体の主鎖に、脂環族が含まれることが好ましい。このようなポリイミド前駆体を含むポリイミド前駆体含有溶液については、後で詳述する。 1. About 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.
工程b)では、前述の工程a)で支持基材上に形成されたポリイミド前駆体含有溶液の塗膜;つまりポリイミド前駆体フィルムを加熱する。具体的には、i)ポリイミド前駆体フィルムを、150℃以下の温度から200℃超まで温度を上昇させながら加熱し、さらにii)得られる透明ポリイミド層のガラス転移温度以上の温度(一定温度)で、一定時間加熱する工程であることが好ましい。 2. About Step b) In 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.
工程a)で塗布するポリイミド前駆体含有溶液には、ポリイミド前駆体と溶剤とが含まれ、必要に応じて離型剤が含まれる。ポリイミド前駆体含有溶液に離型剤が含まれると、透明ポリイミド積層体における透明ポリイミド層と支持基材との剥離性が高まる。また、ポリイミド前駆体含有溶液には、必要に応じて各種添加剤が含まれてもよい。 3. About a polyimide precursor containing solution The polyimide precursor containing solution applied in step a) contains a polyimide precursor and a solvent, and if necessary, a release agent. When 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. Moreover, various additives may be contained in the polyimide precursor containing solution as needed.
ポリイミド前駆体は、テトラカルボン酸成分(A)と、ジアミン成分(B)とを反応させてなる。ポリイミド前駆体含有溶液に含まれるポリイミド前駆体の濃度は、5~50質量%であることが好ましく、より好ましくは10~40質量%である。ポリイミド前駆体の濃度が50質量%を超えると、ポリイミド前駆体含有溶液の粘度が過剰に高くなり、支持基材への塗布が困難となる場合がある。一方、5質量%未満であると、ポリイミド前駆体含有溶液の粘度が過剰に低く、ポリイミド前駆体フィルムを所望の厚みに塗布できない場合がある。また、溶剤の乾燥に時間がかかり、ポリイミドフィルムの製造効率が悪くなる。 3-1. Polyimide precursor The polyimide precursor is obtained by reacting a tetracarboxylic acid component (A) with a diamine component (B). The 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. When the density | concentration of a polyimide precursor exceeds 50 mass%, the viscosity of a polyimide precursor containing solution will become high too much, and the application | coating to a support base material may become difficult. On the other hand, when 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.
ポリイミド前駆体を構成するテトラカルボン酸成分(A)には、下記一般式(a)で表されるテトラカルボン酸二無水物が含まれる。テトラカルボン酸成分(A)には、一般式(a)で表されるテトラカルボン酸二無水物が一種類のみが含まれてもよく、また2種類以上含まれてもよい。
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.
ポリイミド前駆体を構成するジアミン成分(B)には、下記の一般式(b-1)~(b-3)で表されるジアミンが含まれる。ジアミン成分(B)には、下記の一般式(b-1)~(b-3)で表されるジアミンが1種のみ含まれてもよく、また2種以上含まれてもよい。また、ジアミン成分(B)には、一般式(b-1)~(b-3)で表されるジアミン以外のジアミン(b-4)が含まれていてもよい。
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).
<1>p-フェニレンジアミン、m-フェニレンジアミン、p-キシリレンジアミン、m-キシリレンジアミンなどのベンゼン環を1つ有するジアミン;
<2>3,3'-ジアミノジフェニルエーテル、3,4'-ジアミノジフェニルエーテル、4,4'-ジアミノジフェニルエーテル、3,3'-ジアミノジフェニルスルフィド、3,4'-ジアミノジフェニルスルフィド、4,4'-ジアミノジフェニルスルフィド、3,3'-ジアミノジフェニルスルホン、3,4'-ジアミノジフェニルスルホン、4,4'-ジアミノジフェニルスルホン、3,3'-ジアミノベンゾフェノン、4,4'-ジアミノベンゾフェノン、3,4'-ジアミノベンゾフェノン、3,3'-ジアミノジフェニルメタン、4,4'-ジアミノジフェニルメタン、3,4'-ジアミノジフェニルメタン、2,2-ジ(3-アミノフェニル)プロパン、2,2-ジ(4-アミノフェニル)プロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)プロパン、2,2-ジ(3-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ジ(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、1,1-ジ(3-アミノフェニル)-1-フェニルエタン、1,1-ジ(4-アミノフェニル)-1-フェニルエタン、1-(3-アミノフェニル)-1-(4-アミノフェニル)-1-フェニルエタンなどのベンゼン環を2つ有するジアミン;
<3>1,3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(3-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノベンゾイル)ベンゼン、1,3-ビス(4-アミノベンゾイル)ベンゼン、1,4-ビス(3-アミノベンゾイル)ベンゼン、1,4-ビス(4-アミノベンゾイル)ベンゼン、1,3-ビス(3-アミノ-α,α-ジメチルベンジル)ベンゼン、1,3-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン、1,4-ビス(3-アミノ-α,α-ジメチルベンジル)ベンゼン、1,4-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン、1,3-ビス(3-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,3-ビス(4-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,4-ビス(3-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,4-ビス(4-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、2,6-ビス(3-アミノフェノキシ)ベンゾニトリル、2,6-ビス(3-アミノフェノキシ)ピリジンなどのベンゼン環を3つ有するジアミン;
<4>4,4'-ビス(3-アミノフェノキシ)ビフェニル、4,4'-ビス(4-アミノフェノキシ)ビフェニル、ビス[4-(3-アミノフェノキシ)フェニル]ケトン、ビス[4-(4-アミノフェノキシ)フェニル]ケトン、ビス[4-(3-アミノフェノキシ)フェニル]スルフィド、ビス[4-(4-アミノフェノキシ)フェニル]スルフィド、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]エーテル、ビス[4-(4-アミノフェノキシ)フェニル]エーテル、2,2-ビス[4-(3-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2-ビス[3-(3-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパンなどのベンゼン環を4つ有するジアミン;
<5>1,3-ビス[4-(3-アミノフェノキシ)ベンゾイル]ベンゼン、1,3-ビス[4-(4-アミノフェノキシ)ベンゾイル]ベンゼン、1,4-ビス[4-(3-アミノフェノキシ)ベンゾイル]ベンゼン、1,4-ビス[4-(4-アミノフェノキシ)ベンゾイル]ベンゼン、1,3-ビス[4-(3-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,3-ビス[4-(4-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,4-ビス[4-(3-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,4-ビス[4-(4-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼンなどのベンゼン環を5つ有するジアミン;
<6>4,4'-ビス[4-(4-アミノフェノキシ)ベンゾイル]ジフェニルエーテル、4,4'-ビス[4-(4-アミノ-α,α-ジメチルベンジル)フェノキシ]ベンゾフェノン、4,4'-ビス[4-(4-アミノ-α,α-ジメチルベンジル)フェノキシ]ジフェニルスルホン、4,4'-ビス[4-(4-アミノフェノキシ)フェノキシ]ジフェニルスルホンなどのベンゼン環を6つ有するジアミンが含まれる。 Examples of diamines having a benzene ring 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′-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4- Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl)- , 1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) ) -2- (4-Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di ( Diamines having two benzene rings such as 4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane;
<3> 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4- Aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis ( 4-Aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-Amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethyl) Benzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylben) L) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6- A diamine having three benzene rings such as bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine;
<4> 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- ( 4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4 -(3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophene) Noxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3- A diamine having four benzene rings such as hexafluoropropane;
<5> 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3- Aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, , 3-Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4 A diamine having five benzene rings such as bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene;
<6> 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4 Has 6 benzene rings such as' -bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone Diamine is included.
ポリイミド前駆体含有溶液に含まれるポリイミド前駆体は、前述のテトラカルボン酸成分(A)と、前述のジアミン成分(B)とが反応してなるものであれば特に制限されないが、ポリイミド前駆体は、上記一般式(a)で表されるテトラカルボン酸二無水物と一般式(b-1)で表されるジアミンとのポリアミド酸ブロック(下記一般式(G)で表される)と、一般式(a)で表されるテトラカルボン酸二無水物及び、一般式(b-2)、(b-3)、または(b-4)のいずれかで表されるジアミンのポリイミドブロック(下記一般式(H)で表される)とが、結合したブロックポリアミド酸イミドが好ましい。
ポリイミド前駆体含有溶液に含まれる溶剤は、前述のテトラカルボン酸成分(A)及びジアミン成分(B)を溶解可能な溶剤であれば特に制限されない。例えば、非プロトン性極性溶剤または水溶性アルコール系溶剤等でありうる。 3-2. Solvent 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). For example, it may be an aprotic polar solvent or a water-soluble alcohol solvent.
ポリイミド前駆体含有溶液には離型剤が含まれていてもよい。ポリイミド前駆体含有溶液に含まれる離型剤は、支持基材と透明ポリイミド層との離型性を高められるものであれば特に制限されず、公知の内部離型剤でありうる。内部離型剤の例には、脂肪族アルコール、脂肪酸エステル、トリグリセリド類、フッ素系界面活性剤、高級脂肪酸金属塩、リン酸エステル系の離型剤が含まれる。得られる透明ポリイミド層の透明性を阻害し難いとの観点から、リン酸エステル系の離型剤であることが好ましい。リン酸エステル系の離型剤の例には、特開2000-256377号公報に記載の化合物が含まれる。 3-3. Release agent 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. Examples of 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. Examples of the phosphoric ester release agent include compounds described in JP-A No. 2000-256377.
前述のように、ポリイミド前駆体含有溶液には、得られる透明ポリイミド層の透明性及び耐熱性が損なわれない範囲で、各種添加剤が含まれてもよい。各種添加剤の例には、酸化防止剤、熱安定剤、帯電防止剤、難燃剤、紫外線吸収剤が含まれる。 3-4. Other Additives As described above, 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. Examples of various additives include antioxidants, heat stabilizers, antistatic agents, flame retardants, and ultraviolet absorbers.
ポリイミド前駆体含有溶液は、前述のテトラカルボン酸成分(A)と、前述のジアミン成分(B)とを、前述の溶剤中で反応させて得られる。溶剤中のジアミン成分(B)のモル数をx、テトラカルボン酸成分(A)のモル数をyとしたとき、y/xは0.9~1.1であることが好ましく、0.95~1.05であることがより好ましく、0.97~1.03であることがさらに好ましく、0.99~1.01であることが特に好ましい。テトラカルボン酸成分(A)と、ジアミン成分(B)とをこのような比率で重合することにより、ポリイミド前駆体の分子量(重合度)を適度に調整することができる。 3-5. Preparation Method of Polyimide Precursor-Containing Solution 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. When the number of moles of the diamine component (B) in the solvent is x and the number of moles of the tetracarboxylic acid component (A) is y, 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. By polymerizing the tetracarboxylic acid component (A) and the diamine component (B) at such a ratio, the molecular weight (polymerization degree) of the polyimide precursor can be appropriately adjusted.
前述の方法によって得られる透明ポリイミド積層体における、透明ポリイミド層の全光線透過率は、80%以上であり、より好ましくは83%以上であり、さらに好ましくは85%以上である。全光線透過率が80%以上であれば、透明性が必要とされる用途に透明ポリイミド層を適用できる。透明ポリイミド層の全光線透過率は、ポリイミドの種類、前述の工程b)における雰囲気の酸素濃度や圧力等で調整される。特に工程b)の200℃を超える温度領域における雰囲気の酸素濃度を低くしたり、雰囲気の圧力を低くすることで、ポリイミドの酸化が抑制され、透明ポリイミド層の全光線透過率が高まる。全光線透過率は、支持基材から透明ポリイミド層を剥離し、透明ポリイミド層についてJIS-K7105に準じて、光源D65にて測定される。 4). Regarding the transparent polyimide layer 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. in 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.
前述の透明ポリイミド積層体の透明ポリイミド層を、支持基材から剥離して得られる透明ポリイミドフィルムは、種々のフレキシブルデバイスの基板や光学フィルムに適用可能である。また、透明ポリイミドフィルムは全光線透過率が高く、かつ面内位相差が非常に小さいため、特にフレキシブルディスプレイの基板に好適である。フレキシブルディスプレイの例には、タッチパネル、液晶表示ディスプレイ、有機ELディスプレイ等が含まれる。 B. About the use of a transparent polyimide laminated body 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 | substrate and optical film of various flexible devices. Moreover, since 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. Examples of the flexible display include a touch panel, a liquid crystal display, and an organic EL display.
第1の方法は、図2の概略断面図に示されるように、透明ポリイミド積層体12における支持基材11から、透明ポリイミドフィルム(透明ポリイミド層)1’を剥離してから(図2(a))、透明ポリイミドフィルム1’上に素子13を形成する方法である(図2(b))。第1の方法では、剥離した透明ポリイミドフィルム1’を他の基板(図示せず)に貼り合わせてから、透明ポリイミドフィルム1’上に素子13を形成することもできる。 (I) 1st method The 1st method peels transparent polyimide film (transparent polyimide layer) 1 'from the
第2の方法は、図3の概略断面図に示されるように、支持基材11と積層された透明ポリイミド層1’上に素子13を形成した後(図3(a))、支持基材11から透明ポリイミドフィルム(透明ポリイミド層)1’を剥離して(図3(b))、素子13が形成された透明ポリイミドフィルム1’を得る方法である(図3(c))。第2の方法では、素子13の形成時に透明ポリイミド層1’にかかる応力が支持基材11に吸収されやすい。したがって、素子13の形成時に透明ポリイミド層1’が裂けたり割れたりし難い。 (Ii) Second Method As shown in the schematic cross-sectional view of FIG. 3, the second method is to form the
第3の方法は、図4の概略断面図に示されるように、透明ポリイミド積層体12における支持基材11側を他の基板14に貼り合わせてから(図4(a))、透明ポリイミド層1’上に各種素子13を形成し(図4(b))、支持基材11から透明ポリイミドフィルム(透明ポリイミド層)1’を剥離して(図4(c))、素子13が形成されたポリイミドフィルム1’を得る方法である(図4(d))。第3の方法では、他の基板14を透明ポリイミド積層体12と貼り合わせるため、素子13の作製時に透明ポリイミド積層体12が撓まない。したがって、種々の方法で透明ポリイミド層1’上に素子13を形成できる。また、第3の方法でも、素子13の形成時に透明ポリイミド層1’にかかる応力が支持基材11に吸収されやすい。したがって、素子13の形成時に透明ポリイミド層1’が裂けたり割れたりし難い。 (Iii) Third Method As shown in the schematic cross-sectional view of FIG. 4, the third method is performed after the supporting
前述のポリイミド積層体の製造方法は、支持基材と各種樹脂層とを有する樹脂積層体の製造方法にも適用可能である。具体的には、(a)各種樹脂を含むワニスを支持基材上に塗布する工程と、(b)当該ワニスの塗布膜を加熱硬化させる工程とを有する、樹脂積層体の製造方法とすることができる。当該樹脂積層体の製造方法によれば、支持基材から容易に剥離可能な樹脂フィルムが得られる。各種樹脂の例には、前述した以外のポリイミド樹脂(ポリイミド前駆体)、アラミド樹脂、ポリエーテルエーテルケトン樹脂、及びポリエーテルスルホン樹脂等が含まれる。 5. Others 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 | coating the varnish containing various resin on a support base material, and (b) heat-hardening the coating film of the said varnish. Can do. According to the method for producing the resin laminate, a resin film that can be easily peeled off from the support substrate is obtained. Examples of various resins include polyimide resins (polyimide precursors) other than those described above, aramid resins, polyether ether ketone resins, and polyether sulfone resins.
実施例及び比較例で作製した透明ポリイミド積層体を、長さ50mm、幅3.5mmに切出した。この透明ポリイミド積層体を、JIS C-6471に規定される方法に従ってピール強度を測定した。具体的には、透明ポリイミド積層体の短辺の端を把持し、支持基材から剥離角度90°、剥離速度50mm/分で剥離し、剥離時の応力を測定した。応力は、島津製作所製 引張試験機EZ-S、粘着テープ引きはがし試験装置で測定した。 1) Peel strength 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.
実施例及び比較例で作製した透明ポリイミド積層体から透明ポリイミド層を剥離し、当該透明ポリイミド層のイミド化率を、以下のように算出した。なお、IR吸収スペクトルの測定は、FT-IR分光器(FT/IR 300E、日本分光社製)に、多重反射型赤外スペクトル測定装置(ATR PR0410-M 日本分光社製)を取り付けて行った。 2) Imidization rate 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). .
そして、対応するフィルムの比率Bに対する比率Aの値(比率A/比率B)×100(%)を求め、これをイミド化率とした。 About the transparent polyimide layer produced by the Example and the comparative example, IR absorption spectrum was measured, respectively. For each film, 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. On the other hand, 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 IR absorption spectrum of each of these films was measured, and the absorption peak height of 1370 cm −1 with respect to the absorption peak height of 1500 cm −1 (the peak due to C = C stretching vibration of the benzene ring (reference)) was measured in the same manner as described above. The ratio B (CN stretching vibration of imide ring) was calculated.
And the value of the ratio A (ratio A / ratio B) x 100 (%) with respect to the ratio B of the corresponding film was determined, and this was defined as the imidization rate.
実施例及び比較例で作製した透明ポリイミド積層体から透明ポリイミド層を剥離し、当該透明ポリイミド層の溶剤残存量を測定した。測定は、電気炉型熱分解炉(島津製作所製PYR-2A(熱分解温度 320℃))と、ガスクロマト質量分析装置(島津製作所製GC-8A(カラムUniport HP 80/100 KG-02))とを接続し、フィルム中に含まれる溶剤量を特定した。このとき、装置のインジェクタ及びディテクタ温度は200℃、カラム温度は170℃とした。 3) Residual amount of solvent 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. At this time, the injector and detector temperatures of the apparatus were 200 ° C., and the column temperature was 170 ° C.
実施例及び比較例で作製した透明ポリイミド積層体から透明ポリイミド層を剥離し、当該透明ポリイミド層の全光線透過率を測定した。具体的には、JIS-K-7105に準じて、日本電色工業製ヘーズメーターNDH2000にて、光源D65で測定した。 4) Total light transmittance 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.
実施例及び比較例で作製した透明ポリイミド積層体から透明ポリイミド層を剥離し、当該透明ポリイミド層のヘイズを測定した。具体的には、JIS-K-7105に準じて、日本電色工業製ヘーズメーターNDH2000にて、光源D65で測定した。 5) Haze 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.
実施例及び比較例で作製した透明ポリイミド積層体から透明ポリイミド層を剥離し、透明ポリイミド層のb値を測定した。測定には、色彩色差計(測定ヘッド:CM-2500d コニカミノルタ社製)を使用し、C光源・2°、視野・SCIモードにて、校正白色板上で透明ポリイミド層のb値を3回計測した。b値は、3回の計測値の平均値とした。 6) b value 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. For the measurement, 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.
実施例及び比較例で作製した透明ポリイミド積層体から透明ポリイミド層を剥離した。当該透明ポリイミド層の面内位相差を、Uniopt社製光弾性定数測定装置PEL-3A-102CのX,Yモードで測定した。測定温度は25℃、測定波長は550nmとした。具体的には、光弾性定数測定装置でポリイミドフィルムの屈折率を測定し、屈折率が最大となる方向をX軸、このX軸に垂直な方向をY軸とし、X軸方向の屈折率nxと、Y軸方向の屈折率nyとを導き出した。そして、フィルムの厚みをdとしたときに、(nx-ny)×dで表される値を、面内位相差とした。 7) In-plane retardation R0
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., and the measurement wavelength was 550 nm. Specifically, 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. And a refractive index ny in the Y-axis direction. The value represented by (nx−ny) × d, where d is the thickness of the film, was defined as the in-plane retardation.
実施例及び比較例で使用した支持基材の十点平均粗さを、JIS B0601に準拠して測定した。このとき、カットオフ値0.25mm、測定長さ2.5mmとして、支持基材の幅方向の十点平均粗さを、表面粗さ・輪郭形状測定機(サーフコム1400D 東京精密製)で測定した。 8) 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). .
[ジアミン成分]
14BAC:1,4-ビス(アミノメチル)シクロヘキサン
NBDA:ノルボルナンジアミン
ODA:4,4’-ジアミノジフェニルエーテル
CHDA:トランス-1,4-シクロヘキサンジアミン
[テトラカルボン酸成分]
PMDA:ピロメリット酸二無水物
BPDA:3,3',4,4'-ビフェニルテトラカルボン酸二無水物
[溶剤]
DMAc:N,N-ジメチルアセトアミド
NMP:N-メチル-2-ピロリドン Abbreviations of compounds used in Examples and Comparative Examples are as follows.
[Diamine component]
14BAC: 1,4-bis (aminomethyl) cyclohexane NBDA: norbornanediamine ODA: 4,4′-diaminodiphenyl ether CHDA: trans-1,4-cyclohexanediamine [tetracarboxylic acid component]
PMDA: pyromellitic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride [solvent]
DMAc: N, N-dimethylacetamide NMP: N-methyl-2-pyrrolidone
温度計、攪拌機、及び窒素導入管を備えた300mLの5つ口セパラブルフラスコに、14BAC 469.4g(3.3モル)と、DMAc 5761gとを加えて撹拌した。この混合液に、粉体状のBPDA 970.9g(3.3モル)を添加した。BPDAの添加後、120℃に保持したオイルバスに反応容器を5分間浴した。BPDAの添加から約3分後に、塩が析出したが、その後、速やかに溶解した。この混合液を室温でさらに18時間攪拌して、ポリイミド前駆体含有溶液を得た。 (Synthesis Example 1)
To a 300 mL five-necked separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 149.4 g (3.3 mol) of 14BAC and 5761 g of DMAc were added and stirred. To this mixed solution, 970.9 g (3.3 mol) of powdery BPDA was added. After the addition of BPDA, the reaction vessel was bathed in an oil bath maintained at 120 ° C. for 5 minutes. About 3 minutes after the addition of BPDA, the salt precipitated, but then dissolved rapidly. This mixed solution was further stirred at room temperature for 18 hours to obtain a polyimide precursor-containing solution.
温度計、攪拌機、及び窒素導入管及び滴下ロートを備えた300mLの5つ口セパラブルフラスコに、PMDA 39.7g(0.180モル)と、DMAc 130gとを加えて攪拌し、PMDAのスラリーを得た。一方、NBDA 27.8g(0.180モル)とDMAc 27.8gとの混合溶液を準備した。この混合溶液を、前記スラリー中に、温度を一定に保持しながら120分間かけて滴下した。その後、混合液を50℃で5時間攪拌し、ポリイミド前駆体含有溶液を得た。 (Synthesis Example 2)
PMDA 39.7 g (0.180 mol) and DMAc 130 g were added to a 300 mL 5-neck separable flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a dropping funnel, and the PMDA slurry was stirred. Obtained. On the other hand, a mixed solution of 27.8 g (0.180 mol) of NBDA and 27.8 g of DMAc was prepared. This mixed solution was dropped into the slurry over 120 minutes while keeping the temperature constant. Thereafter, the mixed solution was stirred at 50 ° C. for 5 hours to obtain a polyimide precursor-containing solution.
温度計、攪拌機、窒素導入管を備えた300mLの5つ口セパラブルフラスコに、14BAC 14.1g(0.099モル)、NBDA 1.7g(0.011モル)と、DMAc 189gとを加えて撹拌した。この混合液に、粉体状のBPDA 29.1g(0.099モル)、PMDA 2.4g(0.011モル)を添加した。BPDA、PMDAの添加後、120℃に保持したオイルバスに反応容器を5分間浴した。BPDA、PMDAの添加から約3分後に、塩が析出したが、その後、速やかに溶解した。この混合液を室温でさらに18時間攪拌して、ポリイミド前駆体含有溶液を得た。 (Synthesis Example 3)
To a 300 mL five-necked separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube were added 14.1 g (0.099 mol) of 14BAC, 1.7 g (0.011 mol) of NBDA, and 189 g of DMAc. Stir. To this mixed solution, 29.1 g (0.099 mol) of powdery BPDA and 2.4 g (0.011 mol) of PMDA were added. After the addition of BPDA and PMDA, the reaction vessel was bathed in an oil bath maintained at 120 ° C. for 5 minutes. About 3 minutes after the addition of BPDA and PMDA, a salt precipitated, but then it quickly dissolved. This mixed solution was further stirred at room temperature for 18 hours to obtain a polyimide precursor-containing solution.
温度計、攪拌機、及び窒素導入管を備えた300mLの5つ口セパラブルフラスコに、ODA 10.0g(0.050モル)と、DMAc 119gとを加えて攪拌した。この混合液に、粉体状のPMDA 10.9g(0.050モル)を、温度を一定に保持しながら添加した。その後、混合液を50℃で5時間攪拌し、ポリイミド前駆体含有溶液を得た。 (Synthesis Example 4)
In a 300 mL five-necked separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 10.0 g (0.050 mol) of ODA and 119 g of DMAc were added and stirred. To this mixed solution, 10.9 g (0.050 mol) of powdery PMDA was added while keeping the temperature constant. Thereafter, the mixed solution was stirred at 50 ° C. for 5 hours to obtain a polyimide precursor-containing solution.
・アミド酸オリゴマー溶液の合成
温度計、攪拌機、窒素導入管を備えた300mLの5つ口セパラブルフラスコに、CHDA 11.4g(0.100モル)と、溶媒のNMP 116gとを加え、溶液が透明になるまで攪拌した。当該溶液に、BPDA 27.1g(0.092モル)を粉状のまま装入し、反応容器を120℃に保持したオイルバス中に5分間浴した。BPDA装入後しばらくして塩が析出した。その後、塩は溶解し、均一系となって溶液の粘度が増大した。オイルバスを外してから、更に18時間室温で攪拌し、末端にCHDA由来のアミノ基を有するアミド酸オリゴマー溶液を得た。 (Synthesis Example 5)
Synthesis of amic acid oligomer solution To a 300 mL five-necked separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 11.4 g (0.100 mol) of CHDA and 116 g of NMP as a solvent were added. Stir until clear. To this solution, 27.1 g (0.092 mol) of BPDA was charged in powder form, and the reaction vessel was bathed in an oil bath maintained at 120 ° C. for 5 minutes. Some time after the BPDA was charged, salt precipitated. Thereafter, the salt dissolved and became homogeneous and the viscosity of the solution increased. After removing the oil bath, the mixture was further stirred at room temperature for 18 hours to obtain an amic acid oligomer solution having an amino group derived from CHDA at the terminal.
温度計、攪拌機、窒素導入管を備えた300mLの5つ口セパラブルフラスコに、NBDA 11.1g(0.072モル)と、NMP 94.5gとを加え、溶液が透明になるまでて攪拌した。当該溶液に、BPDA 29.4g(0.100モル)を粉状のまま装入し、反応容器を120℃に保持したオイルバス中に5分間浴した。BPDA装入後、一時的に塩が析出した。その後、粘度増大を伴いながら再溶解し均一透明溶液となることを確認した。
当該セパラブルフラスコに冷却管とディーンスターク型濃縮器を取付けて、キシレン 80.0gを反応溶液に追加し、攪拌しながら180℃で4時間、脱水熱イミド化反応させた。当該反応後、キシレンを留去し、末端にBPDA由来の酸無水物構造を有するイミドオリゴマー溶液を得た。 ・ Synthesis of imide oligomer solution To a 300 mL 5-neck separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 11.1 g (0.072 mol) of NBDA and 94.5 g of NMP were added, and the solution was transparent. Stir until. To the solution, 29.4 g (0.100 mol) of BPDA was charged in a powder form, and the reaction vessel was bathed in an oil bath maintained at 120 ° C. for 5 minutes. After the BPDA was charged, salt temporarily precipitated. Thereafter, it was confirmed that the solution was re-dissolved with increasing viscosity and became a uniform transparent solution.
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.
前述のアミド酸オリゴマー溶液 40.0gと、前述のイミドオリゴマー溶液 9.99gとを混合し、高粘度材料撹拌脱泡ミキサ(株式会社ジャパンユニックス社製、製品名:UM-118)にて10分間攪拌し、ブロックポリアミド酸イミド溶液を得た。 -Synthesis | combination of block polyamic-acid imide solution The above-mentioned amic acid oligomer solution 40.0g and the above-mentioned imide oligomer solution 9.99g are mixed, and a high-viscosity material stirring defoaming mixer (The product made by Japan Unix Co., Ltd., product name: UM-118) was stirred for 10 minutes to obtain a block polyamic acid imide solution.
合成例1で調製したポリイミド前駆体含有溶液を、ガラス基板にカプトンテープで固定した宇部興産製のポリイミドフィルム(UPILEX50S(50μm))上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から270℃まで120分かけて昇温(昇温速度2℃/分)し、さらに270℃で2時間保持し、ガラス基板上に透明ポリイミド積層体を作製した。得られた透明ポリイミド層の厚みは30μmであった。
ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.039kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は260℃、全光線透過率は87%、面内位相差(R0)は0.8nm、イミド化率は98%であり、溶剤残存量は0.2質量%であった。 (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 μm)) 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 μm.
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%, and the residual solvent amount is It was 0.2% by mass.
イナートオーブン内の酸素濃度を5.0%に変更した以外は実施例1と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.039kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は261℃、全光線透過率は87%、面内位相差(R0)は0.8nm、イミド化率は98%であり、溶剤残存量は0.2質量%であった。 (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.
昇温速度を10℃/分に変更した以外は実施例1と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.032kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は260℃、全光線透過率は87%、面内位相差(R0)は0.7nm、イミド化率は95%であり、溶剤残存量は0.5質量%であった。 (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 peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.032 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 0.7 nm, the imidization rate is 95%, and the residual solvent amount is It was 0.5 mass%.
イナートオーブンの最高到達温度を280℃に変更し、昇温速度を2℃/分とした以外は実施例3と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.040kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は261℃、全光線透過率は86%、面内位相差(R0)は0.7nm、イミド化率は100%であり、残存溶剤は検出されなかった。 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 peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.040 kN / m.
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.
合成例1で調製したポリイミド前駆体含有溶液を、ガラス基板にカプトンテープで固定した宇部興産製のポリイミドフィルム(UPILEX50S)上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を20%に制御し、30℃から180℃まで75分かけて昇温(昇温速度2℃/分)し、さらに180℃で2時間保持した。その後、サンプルを減圧オーブンに移し、フルバキュームにて減圧度1kPa以下としてから、昇温を開始した。減圧オーブンを30℃から270℃まで60分かけて昇温(昇温速度4℃/分)し、さらに270℃で1時間保持し、ガラス基板上に透明ポリイミド積層体を作製した。
ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.031kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は260℃、全光線透過率は86%、面内位相差(R0)は0.5nm、イミド化率は96%であり、溶剤残存量は0.7質量%であった。 (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. 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%, and the residual solvent amount is It was 0.7 mass%.
合成例2で調製したポリイミド前駆体含有溶液を、ガラス基板にカプトンテープで固定した宇部興産製のポリイミドフィルム(UPILEX50S)上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から300℃まで135分かけて昇温(昇温速度2℃/分)し、さらに300℃で2時間保持し、ガラス基板上に透明ポリイミド積層体を作製した。
ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.029kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は290℃、全光線透過率が88%、面内位相差(R0)は0.3nm、イミド化率は98%であり、溶剤残存量は0.6質量%であった。 (Example 6)
The polyimide precursor-containing solution prepared in Synthesis Example 2 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 is controlled to 0.0%, the temperature is increased from 30 ° C. to 300 ° C. over 135 minutes (temperature increase rate: 2 ° C./min), and further maintained at 300 ° 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 0.029 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%, and the residual solvent amount is It was 0.6 mass%.
使用するポリイミド前駆体含有溶液を合成例3で調整したものに変更し、昇温速度を2℃/分とした以外は実施例1と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.041kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は266℃、全光線透過率が88%、面内位相差(R0)は0.6nm、イミド化率は96%であり、溶剤残存量は0.3質量%であった。 (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%, and the residual solvent amount is It was 0.3% by mass.
合成例1で調製したポリイミド前駆体含有溶液を、ガラス基板にカプトンテープで固定した東海アルミ製のアルミ箔(50μm)上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から270℃まで120分かけて昇温(昇温速度2℃/分)し、さらに270℃で2時間保持し、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.19kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は261℃、全光線透過率が85%、面内位相差(R0)は1.4nm、イミド化率は99%であり、溶剤残存量は0.1質量%であった。 (Reference Example 1)
The polyimide precursor-containing solution prepared in Synthesis Example 1 was coated on a Tokai aluminum aluminum foil (50 μm) 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%, and the residual solvent amount is It was 0.1 mass%.
合成例1で調製したポリイミド前駆体含有溶液100gにデュポン製離型剤ゼレックUNを0.01g配合(固形分に対して500ppm相当)した剥離成分含有ポリイミド前駆体含有溶液を使用したこと以外は実施例8と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.007kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は260℃、全光線透過率が85%、面内位相差(R0)は1.1nm、イミド化率は99%であり、溶剤残存量は0.1質量%であった。 (Reference Example 2)
Implemented except that 100 g of the polyimide precursor-containing solution prepared in Synthesis Example 1 was mixed with 0.01 g of DuPont release agent Zelec UN (corresponding to 500 ppm with respect to the solid content) and the release component-containing polyimide precursor-containing solution was used. In the same manner as in Example 8, a transparent polyimide laminate was produced on a glass substrate. The peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.007 kN / m.
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%, and the residual solvent amount is It was 0.1 mass%.
使用する支持基材をSUS304(50μm)に変更した以外は実施例9と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.009kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は262℃、全光線透過率が86%、面内位相差(R0)は1.2nm、イミド化率は99%であり、溶剤残存量は0.2質量%であった。 (Reference Example 3)
A transparent polyimide laminate was produced on a glass substrate in the same manner as in Example 9 except that the supporting substrate used was changed to SUS304 (50 μm). The peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.009 kN / m.
The glass transition temperature (Tg) of the transparent polyimide film after peeling is 262 ° C., the total light transmittance is 86%, the in-plane retardation (R0) is 1.2 nm, the imidization rate is 99%, and the residual solvent amount is It was 0.2% by mass.
合成例1で調製したポリイミド前駆体含有溶液を、宇部興産製のポリイミドフィルム(UPILEX50S(50μm))上にダイコーターを用いて、連続的に直接流延塗布し、酸素濃度を0.0%に制御した乾燥炉を用いて、段階的に昇温を実施し(昇温速度5℃/分相当)、最高温度270℃まで加熱を実施し、透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.039kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は261℃、全光線透過率が87%、面内位相差(R0)は2.0nm、イミド化率は97%であり、溶剤残存量は0.8質量%であった。 (Example 8)
The polyimide precursor-containing solution prepared in Synthesis Example 1 was continuously and continuously cast onto a polyimide film (UPILEX 50S (50 μm)) 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.
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%, and the residual solvent amount is It was 0.8 mass%.
合成例5で調製したブロックポリアミド酸イミド溶液を、ガラス基板にカプトンテープで固定した宇部興産製のポリイミドフィルム(UPILEX50S(50μm、Rz=0.03μm))上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びブロックポリアミド酸イミドフィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から270℃まで120分かけて昇温(昇温速度2℃/分)し、さらに270℃で2時間保持し、ガラス基板上に透明ポリイミド積層体を作製した。得られた透明ポリイミド積層体の、透明ポリイミド層の厚みは30μmであった。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.030kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は286℃、全光線透過率は85%、ヘイズが1.0%、b値が1.8、面内位相差(R0)は0.9nm、イミド化率は98%であり、溶剤残存量は0.5質量%であった。 Example 9
The block polyamic acid imide solution prepared in Synthesis Example 5 was applied with a doctor blade onto a Ube Industries polyimide film (UPILEX 50S (50 μm, Rz = 0.03 μm)) fixed to a glass substrate with Kapton tape. And the sample which consists of a glass substrate, a support base material, and a block polyamic-acid imide 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 transparent polyimide layer of the obtained transparent polyimide laminate was 30 μm. 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.
使用するポリイミド前駆体含有溶液を合成例4で調整したものに変更し、30℃から300℃まで135分かけて昇温(昇温速度2℃/分)し、300℃で2時間保持した以外は実施例1と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.025kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は検出されず、全光線透過率が78%、面内位相差(R0)は0.9nm、イミド化率は95%であり、溶剤残存量は0.9質量%であった。 (Comparative Example 1)
The polyimide precursor-containing solution to be used was changed to that prepared in Synthesis Example 4, and the temperature was raised from 30 ° C. to 300 ° C. over 135 minutes (temperature increase rate 2 ° C./min), and kept at 300 ° C. for 2 hours. Made a transparent polyimide laminate on the glass substrate in the same manner as in Example 1. The peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.025 kN / m.
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%.
イナートオーブン内の酸素濃度を10.0%に変更した以外は実施例1と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.031kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は259℃、全光線透過率が79%、面内位相差(R0)は0.8nm、イミド化率は97%であり、溶剤残存量は0.5質量%であった。 (Comparative 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%.
イナートオーブンの最高到達温度を230℃に変更した以外は実施例1と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.010kN/mであった。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は250℃、全光線透過率が90%、面内位相差(R0)は0.8nm、イミド化率は78%であり、溶剤残存量は3.0質量%であった。 (Comparative 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 peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.010 kN / m.
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%, and the residual solvent amount is It was 3.0 mass%.
使用する支持基材を三井金属鉱業製の銅箔(NA-DFF(12μm))に変更した以外は実施例1と同様にし、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の銅箔(支持基材)から透明ポリイミド層を引き剥がそうと試みたが、剥がすことが出来なかった。 (Comparative 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 μm)) 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.
合成例1で調製したポリイミド前駆体含有溶液100gにデュポン製離型剤ゼレックUNを0.10g配合(固形分に対して5000ppm相当)した剥離成分含有ポリイミド前駆体含有溶液を、ガラス基板にカプトンテープで固定した東海アルミ製のアルミ箔(支持基材;50μm)上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から270℃まで120分かけて昇温(昇温速度2℃/分)し、さらに270℃で2時間保持した。オーブンから出した透明ポリイミド積層体は支持基材上で透明ポリイミド層が“はじき”により一部凝集しており、製膜困難であることを確認した。 (Comparative Example 5)
A release component-containing polyimide precursor-containing solution in which 0.10 g of DuPont release agent Zelec UN is mixed with 100 g of the polyimide precursor-containing solution prepared in Synthesis Example 1 (equivalent to 5000 ppm with respect to the solid content) is added to a Kapton tape It was coated with a doctor blade on an aluminum foil (support base material: 50 μm) made of Tokai Aluminum fixed in (1). 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 0.0%, the temperature was 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. The transparent polyimide laminate taken out of the oven was confirmed to be difficult to form because the transparent polyimide layer was partially agglomerated by “repelling” on the support substrate.
合成例1で調製したポリイミド前駆体含有溶液を、ガラス基板上に直接ドクターブレードで塗工した。そして、ガラス基板、ポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から270℃まで120分かけて昇温(昇温速度2℃/分)し、さらに270℃で2時間保持し、ガラス基板上に透明ポリイミド層を作製した。得られた透明ポリイミド層の厚みは30μmであった。
ガラス基板から透明ポリイミド層の剥離を試みたが、容易に剥離することは困難であった。そこで、ガラス基板/透明ポリイミド層を蒸留水に浸漬してガラス基板から透明ポリイミドフィルムを剥離した。
剥離後の透明ポリイミドフィルムのガラス転移温度(Tg)は260℃、全光線透過率は87%、面内位相差(R0)は0.8nm、イミド化率は98%であり、溶剤残存量は0.1質量%であった。 (Comparative Example 6)
The polyimide precursor-containing solution prepared in Synthesis Example 1 was applied directly on a glass substrate with a doctor blade. And the sample which consists of a glass substrate 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 layer was produced on the substrate. The thickness of the obtained transparent polyimide layer was 30 μm.
Although an attempt was made to peel off the transparent polyimide layer from the glass substrate, it was difficult to peel off easily. Therefore, 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%, and the residual solvent amount is It was 0.1 mass%.
合成例1で調製したポリイミド前駆体含有溶液を、ガラス基板にカプトンテープで固定した宇部興産製のポリイミドフィルム(UPILEX50S(50μm、Rz=0.03μm))上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から200℃まで85分かけて昇温(昇温速度2℃/分)し、さらに200℃で2時間保持した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.008kN/mであった。 (Comparative Example 7)
The polyimide precursor-containing solution prepared in Synthesis Example 1 was applied with a doctor blade onto a Ube Industries polyimide film (UPILEX50S (50 μm, Rz = 0.03 μm)) 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 0.0%, the temperature was raised from 30 ° C. to 200 ° C. over 85 minutes (temperature increase rate: 2 ° C./min), and further maintained at 200 ° C. for 2 hours. The peel strength of the support base / transparent polyimide layer interface of the transparent polyimide laminate removed from the glass substrate was 0.008 kN / m.
合成例1で調製したポリイミド前駆体含有溶液を、ガラス基板にカプトンテープで固定した宇部興産製のポリイミドフィルム(UPILEX50S(50μm、Rz=0.03μm))上にドクターブレードで塗工した。そして、ガラス基板、支持基材、及びポリイミド前駆体フィルムからなるサンプルをイナートオーブンに入れた。その後、イナートオーブン内の酸素濃度を0.0%に制御し、30℃から270℃まで120分かけて昇温(昇温速度2℃/分)し、さらに270℃で2時間保持し、ガラス基板上に透明ポリイミド積層体を作製した。ガラス基板上から取り外した透明ポリイミド積層体の支持基材/透明ポリイミド層界面のピール強度は0.039kN/mであった。 (Comparative Example 8)
The polyimide precursor-containing solution prepared in Synthesis Example 1 was applied with a doctor blade onto a Ube Industries polyimide film (UPILEX50S (50 μm, Rz = 0.03 μm)) 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 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.
一方、支持基材をアルミ基板とした場合には、支持基材から透明ポリイミド層を剥離する際のピール強度が0.19kN/mと比較的高かった(参考例1)。これに対し、支持基材をアルミ基板とした場合であっても、ポリイミド前駆体含有溶液に離型剤が含まれる(参考例2)とピール強度が大きく低下した。ただし、離型剤の量が多すぎると、ポリイミド前駆体含有溶液を均一に塗布することができなかった(比較例5)。また、SUS板を支持基材とし、ポリイミド前駆体含有溶液に離型剤が含まれる場合には、支持基材から透明ポリイミド層を剥離する際のピール強度が低く、剥離性が良好であった(参考例3)。 When the support substrate is a polyimide film (Examples 1 to 9, Comparative Examples 1 to 3, 7, and 8), 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.
On the other hand, when 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). On the other hand, even when the support substrate was an aluminum substrate, the peel strength was greatly reduced when a release agent was included in the polyimide precursor-containing solution (Reference Example 2). However, when there was too much quantity of a mold release agent, the polyimide precursor containing solution was not able to be apply | coated uniformly (comparative example 5). Moreover, when a SUS plate was used as a supporting base material and the release agent was contained in the polyimide precursor-containing solution, the peel strength when peeling the transparent polyimide layer from the supporting base material was low, and the peelability was good. (Reference Example 3).
1’ 透明ポリイミド層
10 加熱炉
11 支持基材
12 透明ポリイミド積層体
13 素子
14 他の基板
20 塗布装置
21 無端ベルト
30 ロール体
DESCRIPTION OF
Claims (18)
- 支持基材と、前記支持基材上に積層された透明ポリイミド層とを含む透明ポリイミド積層体の製造方法であって、
a)テトラカルボン酸成分及びジアミン成分を反応させてなるポリイミド前駆体と溶剤とを含むポリイミド前駆体含有溶液を、前記支持基材上に塗布する工程と、
b)前記ポリイミド前駆体含有溶液の塗膜からなるポリイミド前駆体フィルムを、前記透明ポリイミド層のガラス転移温度以上で加熱する工程とを含み、
前記透明ポリイミド層は、ガラス転移温度が260℃以上、全光線透過率が80%以上、ヘイズが5%以下、L*a*b表色系におけるb値の絶対値が5以下、かつ面内位相差が10nm以下であり、
前記支持基材から前記透明ポリイミド層を剥離する際のピール強度が0.005~0.20kN/mである、透明ポリイミド積層体の製造方法。 A method for producing a transparent polyimide laminate comprising a support substrate and a transparent polyimide layer laminated on the support substrate,
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 the support substrate;
b) heating a polyimide precursor film comprising a coating film of the polyimide precursor-containing solution above the glass transition temperature of the transparent polyimide layer,
The transparent polyimide layer has a glass transition temperature of 260 ° C. or more, a total light transmittance of 80% or more, a haze of 5% or less, an absolute value of b value in the L * a * b color system of 5 or less, and an in-plane The phase difference is 10 nm or less,
A method for producing a transparent polyimide laminate, wherein a peel strength when peeling the transparent polyimide layer from the support substrate is 0.005 to 0.20 kN / m. - 前記支持基材が、フレキシブル基材である、請求項1に記載の透明ポリイミド積層体の製造方法。 The method for producing a transparent polyimide laminate according to claim 1, wherein the support substrate is a flexible substrate.
- 前記ポリイミド前駆体含有溶液に、離型剤がさらに含まれる、請求項1に記載の透明ポリイミド積層体の製造方法。 The method for producing a transparent polyimide laminate according to claim 1, wherein a release agent is further included in the polyimide precursor-containing solution.
- 前記工程b)の200℃を超える温度領域では、雰囲気の酸素濃度を5体積%以下とする、請求項1に記載の透明ポリイミド積層体の製造方法。 The method for producing a transparent polyimide laminate according to claim 1, wherein the oxygen concentration of the atmosphere is 5% by volume or less in the temperature range exceeding 200 ° C in the step b).
- 前記工程b)の200℃を超える温度領域では、雰囲気を減圧する、請求項1に記載の透明ポリイミド積層体の製造方法。 The method for producing a transparent polyimide laminate according to claim 1, wherein the atmosphere is depressurized in the temperature range exceeding 200 ° C in the step b).
- 前記工程b)は、150℃以下から200℃超まで昇温しながら前記ポリイミド前駆体フィルムを加熱する工程であり、
前記工程b)における150~200℃の温度領域の平均昇温速度を0.25~50℃/分とする、請求項1に記載の透明ポリイミド積層体の製造方法。 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.,
The method for producing a transparent polyimide laminate according to claim 1, wherein the average temperature increase rate in the temperature range of 150 to 200 ° C in the step b) is 0.25 to 50 ° C / min. - 前記ポリイミド前駆体が、
下記一般式(a)で表される1種以上のテトラカルボン酸二無水物を含むテトラカルボン酸成分(A)と、
下記一般式(b-1)~(b-3)で表される化合物からなる群から選ばれる1種以上のジアミンを含むジアミン成分(B)と
を反応させてなる化合物である、請求項1に記載の透明ポリイミド積層体の製造方法。
脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、もしくは縮合多環式芳香族基を示すか、環式脂肪族基が直接もしくは架橋員により相互に連結された非縮合多環式脂肪族基を示すか、または芳香族基が直接もしくは架橋員により相互に連結された非縮合多環式芳香族基を示す)
A tetracarboxylic acid component (A) containing one or more tetracarboxylic dianhydrides represented by the following general formula (a);
2. A compound obtained by reacting a diamine component (B) containing one or more diamines selected from the group consisting of compounds represented by the following general formulas (b-1) to (b-3): The manufacturing method of the transparent polyimide laminated body of description.
- 前記ポリイミド前駆体が、下記一般式(I)で表される繰り返し単位を有し、
一般式(I)における1,4-ビスメチレンシクロヘキサン骨格(X)は、式(X1)で表されるトランス体と、式(X2)で表されるシス体とからなり、
前記トランス体とシス体の含有比(トランス体+シス体=100%)が、60%≦トランス体≦100%、0%≦シス体≦40%である、請求項7に記載の透明ポリイミド積層体の製造方法。
脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、もしくは縮合多環式芳香族基を示すか、環式脂肪族基が直接もしくは架橋員により相互に連結された非縮合多環式脂肪族基を示すか、または芳香族基が直接もしくは架橋員により相互に連結された非縮合多環式芳香族基を示す) The polyimide precursor has a repeating unit represented by the following general formula (I):
The 1,4-bismethylenecyclohexane skeleton (X) in the general formula (I) is composed of a trans isomer represented by the formula (X1) and a cis isomer represented by the formula (X2).
The transparent polyimide laminate according to claim 7, wherein the content ratio of the trans isomer to the cis isomer (trans isomer + cis isomer = 100%) is 60% ≦ trans isomer ≦ 100%, 0% ≦ cis isomer ≦ 40%. Body manufacturing method.
- 前記ポリイミド前駆体が、
下記一般式(G)で表される繰り返し構造単位で構成されるポリアミド酸ブロックと、
下記一般式(H)で表される繰り返し構造単位で構成されるポリイミドブロックと、を有するブロックポリアミド酸イミドである、請求項1に記載の透明ポリイミド積層体の製造方法。
一般式(H)において、R7は、炭素数4~51の2価の基であり、かつ脂肪族基、単環式脂肪族基(但し、1,4-シクロヘキシレン基を除く)、縮合多環式脂肪族基、単環式芳香族基もしくは縮合多環式芳香族基であるか、環式脂肪族基が直接もしくは架橋員により相互に連結された非縮合多環式脂肪族基であるか、または芳香族基が直接もしくは架橋員により相互に連結された非縮合多環式芳香族基である) The polyimide precursor is
A polyamic acid block composed of repeating structural units represented by the following general formula (G);
The manufacturing method of the transparent polyimide laminated body of Claim 1 which is a block polyamic-acid imide which has a polyimide block comprised by the repeating structural unit represented by the following general formula (H).
In the 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 groups are connected to each other directly or by a bridging member) - 前記工程a)は、ロールから繰り出された前記支持基材上に、前記ポリイミド前駆体含有溶液を塗布する工程であり、
前記工程b)は、前記ポリイミド前駆体フィルムの加熱後、前記透明ポリイミド積層体をロールに巻き取るステップを含む、請求項1に記載の透明ポリイミド積層体の製造方法。 The step a) is a step of applying the polyimide precursor-containing solution on the support substrate that has been fed out from a roll.
The said process b) is a manufacturing method of the transparent polyimide laminated body of Claim 1 including the step which winds up the said transparent polyimide laminated body to a roll after the said polyimide precursor film is heated. - 請求項1に記載の製造方法から得られる、透明ポリイミド積層体。 A transparent polyimide laminate obtained from the production method according to claim 1.
- 請求項11記載の透明ポリイミド積層体の支持基材から透明ポリイミド層を剥離して得られる、光学フィルム。 An optical film obtained by peeling a transparent polyimide layer from a support substrate of the transparent polyimide laminate according to claim 11.
- 請求項11記載の透明ポリイミド積層体の支持基材から透明ポリイミド層を剥離し、透明ポリイミドフィルムを得る工程を含む、透明ポリイミドフィルムの製造方法。 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 claim 11 to obtain a transparent polyimide film.
- 請求項11記載の透明ポリイミド積層体の前記透明ポリイミド層上に素子を形成する工程と、
前記素子を形成後の前記透明ポリイミド層を、前記支持基材から剥離する工程とを有する、フレキシブルデバイスの製造方法。 Forming a device on the transparent polyimide layer of the transparent polyimide laminate according to claim 11,
And a step of peeling the transparent polyimide layer after forming the element from the support substrate. - 請求項11記載の製造方法で得られる透明ポリイミドフィルム上に素子を形成する工程を有する、フレキシブルデバイスの製造方法。 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 claim 11.
- 請求項14または15に記載のフレキシブルデバイスの製造方法により得られるタッチパネルディスプレイ。 A touch panel display obtained by the flexible device manufacturing method according to claim 14.
- 請求項14または15に記載のフレキシブルデバイスの製造方法により得られる液晶ディスプレイ。 A liquid crystal display obtained by the flexible device manufacturing method according to claim 14 or 15.
- 請求項14または15に記載のフレキシブルデバイスの製造方法により得られる有機ELディスプレイ。
An organic EL display obtained by the method for producing a flexible device according to claim 14.
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Also Published As
Publication number | Publication date |
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TW201412552A (en) | 2014-04-01 |
TWI613089B (en) | 2018-02-01 |
CN104582960A (en) | 2015-04-29 |
KR20150038080A (en) | 2015-04-08 |
JPWO2014041816A1 (en) | 2016-08-18 |
CN104582960B (en) | 2017-03-08 |
JP6265902B2 (en) | 2018-01-24 |
KR101692648B1 (en) | 2017-01-03 |
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