CN106486497B - Polyimide-based plate film with functional layer, method for producing same, and long polyimide laminate - Google Patents

Polyimide-based plate film with functional layer, method for producing same, and long polyimide laminate Download PDF

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CN106486497B
CN106486497B CN201610796862.9A CN201610796862A CN106486497B CN 106486497 B CN106486497 B CN 106486497B CN 201610796862 A CN201610796862 A CN 201610796862A CN 106486497 B CN106486497 B CN 106486497B
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polyimide
film
layer
functional layer
laminate
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CN106486497A (en
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林信行
平石克文
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • 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
    • B32B27/08—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 of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/76—Making of isolation regions between components
    • H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1262—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
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  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Moulding By Coating Moulds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides a polyimide substrate film with a functional layer, which can prevent foreign matters from being mixed into the polyimide substrate film, has good stripping performance from a carrier film and is provided with the functional layer on the polyimide substrate film, a manufacturing method thereof and a long polyimide laminated body. A method for producing a polyimide base plate film with a functional layer, comprising applying a 1 st solution to a continuously supplied carrier to perform a 1 st heat treatment, applying a 2 nd solution to perform a 2 nd heat treatment, thereby obtaining a long polyimide laminate having a 1 st cured polyimide layer and a 2 nd cured polyimide layer, and then forming a functional layer on the polyimide base plate film and separating the carrier film by using one of the cured polyimide layers as the polyimide base plate film and the other as the carrier film, thereby obtaining a polyimide base plate film having a functional layer.

Description

Polyimide-based plate film with functional layer, method for producing same, and long polyimide laminate
Technical Field
The present invention relates to a polyimide-based sheet film with a functional layer, a method for producing the same, and a long polyimide laminate, and more particularly, to a method for producing a polyimide-based sheet film with a functional layer for forming a functional layer for organic EL illumination including flexible displays such as liquid crystal display devices and organic Electroluminescence (EL) displays, electronic paper, touch panels, solar cells, color filters, and the like, and a long polyimide-based sheet film with a functional layer, and to a long polyimide laminate with a functional layer and a long polyimide laminate with a functional layer for obtaining such a long polyimide-based sheet film with a functional layer.
Background
Display devices such as liquid crystal display devices and organic EL display devices are used for various display applications ranging from large displays such as televisions to small displays such as mobile phones, personal computers, and smart phones. As a representative display device, there is an organic EL display device, for example, which is manufactured by forming a thin Film transistor (hereinafter, tft (thin Film transistor)) on a glass substrate as a supporting substrate, sequentially forming an electrode, a light-emitting layer, and an electrode, and finally hermetically sealing the electrodes with another glass substrate, a multilayer Film, or the like.
Here, by replacing the glass substrate as the support base material with a resin substrate, it is possible to realize a thin, lightweight, and flexible display device, and to further expand the applications of the display device.
For example, patent document 1 relates to an invention of a polyimide useful as a plastic substrate for a flexible display and a precursor thereof, and reports that a polyimide obtained by reacting various diamines with tetracarboxylic acids containing an alicyclic structure such as cyclohexylphenyltetracarboxylic acid has excellent transparency. In addition, attempts have been made to reduce the weight by using a flexible resin as a supporting base material, and for example, non-patent documents 1 and 2 below propose organic EL display devices in which a polyimide having high transparency is applied to a supporting base material.
As described above, a resin substrate such as polyimide is known to be effective as a flexible substrate for a flexible display. However, since resin substrates are generally inferior to glass in dimensional stability, transparency, heat resistance, moisture resistance, gas barrier properties, and the like, many studies have been conducted at present.
For example, non-patent document 3 proposes the following method: after a predetermined functional layer is formed on a resin substrate coated and fixed on glass, a Laser beam is irradiated from the glass side by a method called an electron beam Laser release (EPLaR) process, and the resin substrate having the functional layer is forcibly separated from the glass.
Non-patent document 4 proposes the following method: a polyamic acid (polyimide precursor) solution is applied to a glass via a release layer and cured, and after a predetermined functional layer is provided on the obtained polyimide substrate, the polyimide substrate is released from the glass. In this method, a polyamic acid solution is applied to the surface of the release layer, the peripheral portion of the cured polyimide substrate is directly fixed to the glass in advance, a notch is cut in the portion where the functional layer is formed so that the peripheral portion remains on the glass, and the polyimide substrate formed with the release layer interposed therebetween is separated from the glass.
The techniques disclosed in non-patent documents 3 and 4 are each configured to ensure the operability or dimensional stability of a resin substrate by forming the resin substrate on glass and forming a functional layer on the resin substrate. However, these methods have a problem of low productivity, etc., because special means are employed for separating the resin substrate from the glass. That is, in the method using the EPLaR process described in non-patent document 3, it takes time to separate the resin substrate from the glass, and the surface properties of the resin substrate may be adversely affected. In addition, in the method described in non-patent document 4, the number of steps is increased, and a region that cannot be used as a resin substrate is generated, which results in waste. Therefore, it is strongly desired to develop a technique that can effectively utilize the advantages of the resin substrate and can be used as a means contributing to the industrial aspect.
As a method for solving such a problem, a polyimide laminate is disclosed which has a polyimide film on the back surface side of a polyimide substrate instead of glass, has a specific performance at the interface between the polyimide substrate and the polyimide film, and can be separated after forming a predetermined functional layer on the front surface side of the polyimide substrate (see patent document 2). This polyimide laminate uses a polyimide film as a support base material instead of the glass in non-patent document 3 or non-patent document 4, and a polyimide substrate is formed on the support base material by applying a polyamic acid solution to the surface of the polyimide film and performing a heat treatment. Further, according to the polyimide laminate obtained in the above-described manner, the handling property, the dimensional stability, and the like can be secured, and the polyimide substrate can be easily separated from the support base material to form the polyimide film, and therefore, the polyimide laminate can be suitably used for manufacturing a touch panel, a display device, and the like.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent application laid-open No. 2008-231327
[ patent document 2] Japanese patent application laid-open No. 2014-61685
[ non-patent document ]
[ non-patent document 1] S. An et al (S.An et. al.), [ 2.8-inch WQVGA Flexible active matrix organic light emitting diode (2.8-inch WQVGA Flexible AMOLED Using High Performance Low temperature polysilicon TFT on Plastic substrate ] SID, 2010 abstract (DIGEST), p706(2010)
[ non-patent document 2] Dashi et al (Oishi et al), [ Transparent polyimide for Flexible display (Transparent PI for Flexible display) ], IDW 11FLX2/FMC4-1
Non-patent document 3 e.i. hashow (e.i. haskal et al.) "manufacture of Flexible organic light emitting diode display (Flexible OLED display large with the EPLaR Process) using EPLaR Process," european display institute (proc. eurodisplay)07, pp.36-39(2007)
Non-patent document 4 Cheng-Chung Lee et al, a Novel way of manufacturing Flexible Active matrix displays (a Novel Approach to Make Flexible Active matrix displays), SID10 Digest (Digest), pp.810-813(2010)
Disclosure of Invention
[ problems to be solved by the invention ]
According to the method described in patent document 2, since the polyimide film can be formed by easily separating the polyimide substrate from the supporting base material while securing the handling property, the dimensional stability, and the like, it is considered that the application of the resin substrate can be facilitated instead of the conventional glass substrate. However, in the case of obtaining a polyimide substrate film by applying a polyamic acid (polyimide precursor) solution or a polyimide resin solution onto a polyimide film as a support substrate and heating the applied polyimide resin solution as in the method described in patent document 2, foreign matter such as particles may be directly mixed into the polyimide substrate film if the foreign matter adheres to the polyimide film as the support substrate.
For example, in a manufacturing process of a flexible element such as a liquid crystal display device, an organic EL display, an organic EL lighting, electronic paper, a touch panel, a solar cell, a color filter, or the like, a highly clean environment is required, and if even minute dust or the like is present, there is a possibility that the characteristics of the flexible element are significantly degraded due to the contamination thereof. Further, as the performance of the flexible element is improved, the flexible element is miniaturized, and the thickness of the flexible element is reduced, the polyimide substrate film itself is required to be thin, but if the polyimide substrate film is thin, the polyimide substrate film may be damaged in the process of peeling from the supporting substrate, and there is room for further improvement and study in view of the peeling property.
Therefore, the present inventors have repeatedly studied the above-described problems, and as a result, have found that: the present inventors have found that a long polyimide laminate in which a carrier film and a polyimide substrate film are laminated can be obtained by applying a first solution 1 and a second solution 2 containing a polyimide precursor or a polyimide resin solution to a carrier and performing the first heat treatment and the second heat treatment, respectively, whereby foreign matter can be prevented as much as possible, the carrier film and the polyimide substrate film have good releasability, and the long polyimide laminate can be suitably used for the production of a flexible element, and have completed the present invention.
Accordingly, an object of the present invention is to provide a method for producing a functional layer-equipped polyimide substrate film which can prevent the contamination of foreign substances into the polyimide substrate film and has good peelability from the carrier film and which has a functional layer on the polyimide substrate film, and a functional layer-equipped polyimide substrate film obtained by the method.
Another object of the present invention is to provide a polyimide laminate for obtaining the polyimide substrate film with a functional layer, and a polyimide laminate with a functional layer.
[ means for solving problems ]
That is, the gist of the present invention is as follows.
(1) A method for producing a polyimide-based plate film with a functional layer, wherein:
a method for producing a long polyimide laminate comprising a first polyimide cured layer composed of a first solution (1) and a second polyimide cured layer composed of a second solution (2) is provided, the first polyimide cured layer and the second polyimide cured layer being separated from a continuously supplied carrier in the longitudinal direction of the carrier, the second polyimide cured layer being formed from the first polyimide cured layer and the second polyimide cured layer, respectively, by applying a first solution (1) containing a polyimide precursor or a polyimide resin solution and performing a first heat treatment (1) to form a tack-free surface on at least the surface of the first solution, and applying a second solution (2) containing a polyimide precursor or a polyimide resin solution and performing a second heat treatment (2) to obtain a long polyimide laminate,
one of the 1 st polyimide cured layer and the 2 nd polyimide cured layer of the long polyimide laminate is set as a polyimide substrate film, and the other is set as a carrier film, and after a functional layer is formed on the polyimide substrate film, the carrier film is separated to obtain a polyimide substrate film having a functional layer.
(2) The method for producing a polyimide-based plate film with a functional layer according to (1), wherein the functional layer is formed on the polyimide-based plate film while continuously forming the functional layer on the polyimide-based plate film while winding the long polyimide laminate around a winding roll, or the functional layer is formed on the polyimide-based plate film while cutting the polyimide laminate into sheets of a predetermined length and for each sheet of the polyimide laminate while winding the polyimide laminate.
(3) The method for producing a polyimide-based plate film with a functional layer according to (1) or (2), wherein the carrier is separated before the 2 nd heat treatment is performed or after the 2 nd heat treatment is performed in the process of obtaining the long polyimide laminate.
(4) The method for producing a polyimide-based plate film with a functional layer according to any one of (1) to (3), wherein the carrier is a metal roller, an endless belt (endless belt), or a long base material wound in a roll shape.
(5) The method for producing a polyimide-based board film with a functional layer according to any one of (1) to (4), wherein the carrier film contains a 1 st cured polyimide layer, and the polyimide-based board film contains a 2 nd cured polyimide layer.
(6) The method for producing a polyimide-based board film with a functional layer according to any one of (1) to (4), wherein the polyimide-based board film includes a 1 st cured polyimide layer, and the carrier film includes a 2 nd cured polyimide layer.
(7) The method for producing a polyimide-based plate film with a functional layer according to any one of (1) to (6), wherein a 1 st solution containing a polyimide resin solution is applied to the carrier, and a 1 st heat treatment is performed at a maximum temperature of 60 ℃ to 300 ℃, thereby forming a non-adhesive surface on the surface of the 1 st solution.
(8) The method for producing a polyimide substrate film with a functional layer according to any one of (1) to (6), wherein a 1 st solution containing a polyimide precursor is applied to the carrier, and a 1 st heat treatment is performed at a maximum temperature of 100 ℃ to 450 ℃ to form a 1 st cured polyimide layer composed of the 1 st solution.
(9) The method for producing a polyimide-based plate film with a functional layer according to any one of (1) to (8), wherein the maximum temperature of the heat treatment in the 2 nd heat treatment is 100 ℃ to 450 ℃.
(10) The method for producing a polyimide substrate film with a functional layer according to any one of (1) to (9), wherein the interlayer adhesion strength between the 1 st cured polyimide layer and the 2 nd cured polyimide layer is 1 to 20N/m, and the thickness of the 1 st cured polyimide layer or the 2 nd cured polyimide layer as the polyimide substrate film is 1 to 50 μm.
(11) The method for producing a polyimide substrate film with a functional layer according to any one of (1) to (10), wherein the polyimide substrate film has a total light transmittance of 80% or more in the 1 st cured polyimide layer or the 2 nd cured polyimide layer.
(12) The method for producing a polyimide-based plate film with a functional layer according to any one of (1) to (11), wherein the carrier comprises a long base material wound in a roll shape, and the long base material is a polyimide film, a SUS foil, a copper foil, or a composite of two or more of these laminated.
(13) The method for producing a polyimide-based plate film with a functional layer according to any one of (1) to (12), wherein the 1 st polyimide cured layer is formed by coating two or more kinds of the 1 st solutions containing a polyimide precursor or a polyimide resin solution by superposition coating.
(14) The method for producing a polyimide-based plate film with a functional layer according to any one of (1) to (12), wherein the second polyimide cured layer is formed by coating two or more kinds of second solutions containing a polyimide precursor or a polyimide resin solution by superposition coating.
(15) A long polyimide laminate with functional layers, wherein: a functional layer is continuously formed on a polyimide substrate film in the longitudinal direction of a long polyimide laminate in which the polyimide substrate film and the polyimide substrate film are laminated, the carrier film including a cured polyimide layer obtained by curing one of a 1 st solution and a 2 nd solution containing a polyimide precursor or a polyimide resin solution, the polyimide substrate film including a cured polyimide layer obtained by curing the other of the 1 st solution and the 2 nd solution containing a polyimide precursor or a polyimide resin solution, the polyimide substrate film having a thickness of 1 [ mu ] m to 50 [ mu ] m and a total light transmittance of 80% or more, the interface with the carrier film having a surface roughness with an arithmetic mean roughness Ra of 0nm to 5nm, and the interlayer adhesive strength between the carrier film and the polyimide substrate film being 1N/m to 20N/m.
(16) The long polyimide laminate with a functional layer according to (15), wherein the functional layer is an Indium Tin Oxide (ITO) film.
(17) The long polyimide laminate with a functional layer according to (15), wherein the functional layer is a TFT.
(18) The long polyimide laminate with a functional layer according to the item (15), wherein the functional layer is a layer containing one or a combination of two or more selected from the group consisting of a transparent conductive layer, a wiring layer, a conductive layer, a gas barrier layer, a thin film transistor, an electrode layer, a light-emitting layer, an adhesive layer, a transparent resin layer, a color filter resist, and a hard coat layer.
(19) A long polyimide laminate in which a carrier film and a polyimide substrate film are laminated, wherein the carrier film includes a cured polyimide layer obtained by curing one of a 1 st solution and a 2 nd solution containing a polyimide precursor or a polyimide resin solution, the polyimide substrate film includes a cured polyimide layer obtained by curing the other of the 1 st solution and the 2 nd solution containing a polyimide precursor or a polyimide resin solution, the long polyimide laminate has an interlayer adhesion strength between the carrier film and the polyimide substrate film of 1 to 20N/m, a thickness of the polyimide substrate film of 1 to 50 [ mu ] m, and a total light transmittance of 80% or more.
(20) A long polyimide-based plate film with a functional layer, wherein: a functional layer is continuously formed in the longitudinal direction of a long polyimide substrate film including a polyimide cured layer obtained by curing a solution containing a polyimide precursor or a polyimide resin solution, the polyimide substrate film has a thickness of 1 to 50 [ mu ] m, a total light transmittance of 80% or more, and a surface on the opposite side of the functional layer has a surface roughness with an arithmetic mean roughness Ra of 0 to 5 nm.
[ Effect of the invention ]
According to the present invention, a polyimide substrate film with a functional layer, which is capable of preventing foreign matter from being mixed into a polyimide substrate film, has good peelability from a carrier film, and includes a functional layer on the polyimide substrate film, can be obtained. Among them, polyimide-based film is excellent in heat resistance and applicable to a heat treatment process at high temperature, and thus is used for manufacturing various flexible elements using a functional layer.
In addition, in the process of obtaining such a polyimide substrate film with a functional layer, in the present invention, since the functional layer is formed on the polyimide substrate film constituting the polyimide laminate after the long polyimide laminate is obtained, the handling (handleability) and dimensional stability and the like can be ensured.
Drawings
Fig. 1 is a schematic explanatory view showing a roll-to-roll type coating, drying and curing apparatus used in a process of obtaining a polyimide laminate.
Fig. 2 is a schematic explanatory view showing an endless belt type coating, drying and curing apparatus used in the process of obtaining a polyimide laminate.
Fig. 3 is a schematic explanatory view showing a metal drum type coating, drying and curing apparatus used in the process of obtaining a polyimide laminate.
Fig. 4 is a schematic explanatory view showing a roll-to-roll continuous manufacturing apparatus for forming a functional layer on a polyimide laminate.
Description of the symbols
1: rolling out roller (rolling out part)
2: long base material (conveying body)
3: conveying roller (guide roller)
4: no. 1 Moro pump
5: 1 st Heat treatment apparatus
6: 2 nd Moro pump
7: no. 2 Heat treatment apparatus
8: polyimide laminate
9: winding roll for carrier (winding part)
10: winding roll (winding part) for polyimide laminate
11: annular belt (carrying body)
12: metal roller (carrying body)
13: rolling out roller (rolling out part)
14: conveying roller (guide roller)
15: processing section
16: polyimide laminate with functional layer
17: winding roll (winding part)
Detailed Description
The present invention will be described in detail below.
In the present invention, first, a 1 st solution containing a polyimide precursor or a polyimide resin solution is applied to a continuously supplied transfer body to perform a 1 st heat treatment, thereby forming a non-adhesive surface at least on the surface of the 1 st solution, and then a 2 nd solution containing a polyimide precursor or a polyimide resin solution is applied to the continuously supplied transfer body to perform a 2 nd heat treatment, thereby obtaining a long polyimide laminate which includes a 1 st cured polyimide layer made of the 1 st solution and a 2 nd cured polyimide layer made of the 2 nd solution and is separated from the transfer body with the traveling direction of the transfer body being the longitudinal direction.
In the present invention, the continuously supplied transfer member is used in order to laminate the 1 st cured polyimide layer and the 2 nd cured polyimide layer by a so-called casting method using the 1 st solution and the 2 nd solution containing the polyimide precursor or the polyimide resin solution, and more specifically, in order to obtain a long polyimide laminate in which these cured polyimide layers are laminated.
That is, a polyimide laminate is a long laminated film that is long in the longitudinal Direction (MD) with respect to the Transverse Direction (TD), and is obtained by applying a 1 st solution to a continuously supplied carrier, performing a 1 st heat treatment to form at least a non-adhesive surface, and applying a 2 nd solution to the non-adhesive surface, and performing a 2 nd heat treatment. In the case of such a long polyimide laminate, the polyimide laminate can be conveyed by a roll-to-roll process in the subsequent step, and for example, after being temporarily wound around a winding roll, the polyimide laminate can be continuously formed into a functional layer while being wound off. Therefore, for example, compared to a case where a sheet-like polyimide laminate is obtained using a intermittently supplied carrier and the functional layer is formed by a batch process, the number of steps is reduced, so that the possibility of mixing foreign matter can be eliminated as much as possible, and a flexible element using the functional layer can be efficiently manufactured.
The conveying body to be continuously supplied is not particularly limited, and examples thereof include: metal cylinders, endless belts, long substrates rolled into a roll, and the like. Among these, from the viewpoint of productivity, an endless belt or a long base material wound in a roll form is preferably used, and a long base material wound in a roll form is more preferred. Among them, in the case of a long base material wound in a roll shape, it is preferable that the longer the MD side is, the longer the long polyimide laminate can be obtained, but from the viewpoint of productivity and the like, (the length of the MD side)/(the length of the TD side) is preferably 50 or more, and more preferably 2000 or more. In addition, in the case of the endless belt, the longer the MD side, the more excellent the productivity, but on the other hand, the more expensive the apparatus becomes and the size or weight of the apparatus increases. In view of the balance between these, the length of the endless belt is preferably about 10m to 50 m.
Here, the material forming the carrier body may be at least a temperature that can withstand the 1 st heat treatment for forming the non-adhesive surface by applying the 1 st solution. Specifically, in the case of a long base material wound in a roll shape, there are included: polyimide films, SUS foils, copper foils, and the like, which are excellent in flexibility in addition to strength and heat resistance, may be used as a composite of these. Among them, a polyimide film is preferable. In the case of the endless belt, it is preferably made of SUS.
Then, a 1 st solution containing a polyimide precursor or a polyimide resin solution is applied to a continuously supplied transfer body and subjected to a 1 st heat treatment, thereby forming a non-stick surface in a non-stick state on at least the surface of the 1 st solution. Here, the non-stick state means a state where the object does not adhere to a contact object in contact with the surface of the object, and for example, a state where the composition of the 1 st solution does not adhere to the tip of a finger when the object is contacted with the finger after the 1 st heat treatment after the 1 st solution is applied.
In order to form the 1 st solution applied to the carrier in at least a non-tacky state, the 1 st solution is dried by the 1 st heat treatment so that at least a part of the solvent in the applied 1 st solution is volatilized. In this case, if the 1 st solution is a polyimide resin solution, at least a part of the imide may be formed. If the 1 st heat treatment is insufficient, the polyimide film may be mixed with the 2 nd solution without forming a non-adhesive surface, and then swelling (swelling) may occur in the polyimide laminate, or the polyimide film and the carrier film may not be separated. In addition, the conveyance body may not be separated thereafter, as the case may be.
The 1 st heat treatment differs depending on the type of the 1 st solution used, but when the 1 st solution contains a polyimide resin solution, the 1 st heat treatment is preferably performed at a maximum temperature of 60 to 300 ℃, more preferably 150 to 250 ℃ because imidization is not required and the solvent is merely required to be volatilized, and thus a non-stick surface is preferably formed on the surface of the 1 st solution applied to the carrier. In this case, the 1 st solution which is brought into a non-viscous state by drying in the 1 st heat treatment is preferably at a solid content concentration of about 95 to 99.5% by mass, more preferably at 99 to 99.5% by mass.
On the other hand, in the case where the 1 st solution contains a polyimide precursor, it is preferable that at least the surface thereof is imidized. From this viewpoint, the 1 st polyimide cured layer composed of the 1 st solution may be formed by performing the 1 st heat treatment at the highest temperature of preferably 100 to 450 ℃, more preferably 180 to 360 ℃. In this case, it is preferable that the polyimide precursor is "substantially completely imidized" to form the 1 st polyimide cured layer. The term "substantially complete imidization" as used herein means a state in which the imidization rate is 90% or more. In this case, it is necessary to perform the heat treatment at a temperature higher than the temperature at which the non-stick state is formed by drying. By performing substantially complete imidization, the polyimide substrate film and the carrier film become more easily separable. In this case, the maximum temperature is preferably 300 ℃ to 360 ℃. Furthermore, the first solution 1 containing the polyimide precursor may be imidized by adding a so-called "imidization catalyst" such as pyridine, acetic anhydride, or N-methylimidazole. By adding an imidization catalyst, imidization can be easily performed even at a relatively low temperature.
When the "substantially complete imidization" is performed, the solid content concentration of the 1 st solution is substantially 100% by mass. However, if the heat treatment is performed rapidly, the solvent is rapidly volatilized from the 1 st solution, and there is a possibility that the 1 st solution applied to the carrier may be foamed or the like. Therefore, in the 1 st heat treatment, it is desirable to increase the temperature in stages from a relatively low temperature state before the maximum temperature is reached. In this case, a method using a continuous heat treatment apparatus including a plurality of furnaces and set such that the temperature becomes higher in stages from the furnace on the sample inlet side to the furnace on the sample outlet side can be preferably cited. As another method, the following methods can be preferably cited: the sheet is dried in advance by a heat treatment apparatus at a maximum temperature of 90 to 180 ℃ and then subjected to heat treatment in another heat treatment apparatus within the above-mentioned maximum temperature range (post heat treatment). In the latter case, the post heat treatment temperature is a temperature higher than the pre heat treatment temperature.
In addition, when the 1 st solution is applied to the carrier, a known application method can be used. Specifically, there may be mentioned: a knife coater, a die coater, a lip coater, and the like are preferred because they are closed and have a wide viscosity range that can be handled.
After at least an adhesive surface is formed on the surface of the 1 st solution applied to the carrier as described above, the 2 nd solution containing a polyimide precursor or a polyimide resin solution is applied and the 2 nd heat treatment is performed, thereby forming a 1 st cured polyimide layer made of the 1 st solution and a 2 nd cured polyimide layer made of the 2 nd solution. In the 2 nd heat treatment, the solvent of the applied 2 nd solution is dried to be temporarily made non-stick, and then the 1 st cured polyimide layer and the 2 nd cured polyimide layer are formed (in the case where the 1 st cured polyimide layer is formed in the 1 st heat treatment, the 2 nd cured polyimide layer is formed in the 2 nd heat treatment). After the temporary non-stick state is formed, the 2 nd cured polyimide layer (or the 1 st cured polyimide layer and the 2 nd cured polyimide layer) is formed, whereby the releasability at the interface of these cured polyimide layers can be further improved.
With respect to this 2 nd heat treatment, the heat treatment conditions to form the 2 nd solution into a non-stick state are the same as those in the previous 1 st heat treatment to form the 1 st solution into a non-stick state. In addition, after the 2 nd polyimide cured layer (or the 1 st polyimide cured layer and the 2 nd polyimide cured layer) is formed, in the case where the 2 nd solution contains a polyimide precursor, the same heat treatment conditions as in the above-described "substantially complete imidization" in the 1 st heat treatment are preferably set so that the maximum temperature of the heat treatment in the 2 nd heat treatment is 100 to 450 ℃. More preferably from 180 ℃ to 360 ℃, still more preferably from 300 ℃ to 360 ℃. On the other hand, when the 2 nd solution contains a polyimide resin solution, the maximum temperature of the heat treatment is preferably 150 to 250 ℃.
By such a 2 nd heat treatment, a long polyimide laminate which includes the 1 st cured polyimide layer and the 2 nd cured polyimide layer and is separated from the conveyance body with the traveling direction of the conveyance body being the longitudinal direction can be obtained. Here, in the process of obtaining a long polyimide laminate, the carrier may be separated before the 2 nd heat treatment is performed, or may be separated after the 2 nd heat treatment is performed. Fig. 1 to 3 schematically show the state until a long polyimide laminate is obtained. Fig. 1 shows an example of a case where a long base material 2 wound in a roll shape is used as a carrier, and here, after a 2 nd solution applied by a 2 nd mohno pump 6 is applied by a lip coater (not shown) and a 2 nd heat treatment is performed by a 2 nd heat treatment apparatus 7, the long base material 2 is separated. Fig. 2 shows an example of a case where the endless belt 11 is used as a conveyance body, and fig. 3 shows an example of a case where the metal drum 12 is used as a conveyance body, and in both cases, the 1 st solution applied by the 1 st mohno pump 4 is applied by a lip coater (not shown in the drawing) and subjected to the 1 st heat treatment by the 1 st heat treatment apparatus 5, and then the conveyance body (the endless belt 11 and the metal drum 12) is separated. In order to separate the carrier before the 2 nd heat treatment in this manner, it is preferable that the 1 st cured polyimide layer is formed by the 1 st heat treatment in advance, and the adhesive strength between the carrier and the 1 st cured polyimide layer is preferably 1 to 100N/m, more preferably 10 to 50N/m, including the case where the carrier is separated after the 2 nd heat treatment. The 1 st heat treatment refers to a heat treatment performed by applying the 1 st solution, and the 2 nd heat treatment refers to a heat treatment performed after applying the 2 nd solution, and these may include a plurality of heat treatments. In the figure, arrows indicate the traveling direction of the conveyance body and the like.
As a preferred mode in the process of obtaining a long polyimide laminate, as shown in fig. 1, a Roll-To-Roll (RTR) type coating, drying and curing apparatus including a wind-off Roll (wind-off section) 1, a lip coater (not shown), heat treatment apparatuses (1 st heat treatment apparatus 5 and 2 nd heat treatment apparatus 7) including a continuous drying furnace and a continuous furnace, and a wind-up Roll (wind-up section) 9 and a wind-up Roll (wind-up section) 10 for a carrier and a polyimide laminate may be used. That is, the long base material 2 wound in a roll shape is attached to a wind-off roll (wind-off section) 1, and while being wound off, the 1 st solution and the 2 nd solution applied by the mono pump 4 and the mono pump 6 are applied by a lip coater, and heat treatment is performed to form the polyimide laminate 8 on the long base material 2. Then, the long base material 2 and the polyimide laminate 8 are separated from each other, and the long base material 2 and the polyimide laminate 8 are wound in a roll shape by the winding rollers (winding portions) 9 and 10. The continuous drying furnace is a plurality of drying furnaces connected to each other, and the temperature of each drying furnace can be individually adjusted. Preferably, the set temperature of the drying furnace is set to be higher in stages from the furnace on the unwinding side to the furnace on the winding side. For example, the furnace on the unwinding side is set to 130 ℃, the furnace on the winding side is set to 400 ℃, and the furnace on the unwinding side and the furnace on the winding side are set to any one temperature of 130 ℃ to 400 ℃. The continuous furnace is a furnace in which two or more furnaces are connected and the temperature of each furnace can be individually adjusted. Preferably, the set temperature of the furnace is set to be higher in stages from the furnace on the unwinding side to the furnace on the winding side. For example, the furnace on the unwinding side is set to 130 ℃, the furnace on the winding side is set to 400 ℃, and the furnace on the unwinding side and the furnace on the winding side are set to any one temperature of 130 ℃ to 400 ℃.
After the polyimide laminate is formed on the carrier, the polyimide laminate is peeled off from the carrier in the coating, drying and curing apparatus, and the long base material is wound in a roll shape in the winding section for the long base material, and the polyimide laminate is wound in a roll shape in the winding section for the polyimide laminate. In this way, the work efficiency in the subsequent step of forming the functional layer by conveying the wound polyimide laminate can be improved. Further, the handling efficiency is also good when the wound conveyance body is disposed of or reused. Alternatively, after the polyimide laminate is formed on the long base material, the long base material and the polyimide laminate in a state in which these are laminated are wound into a roll shape by another winding section, these are wound out by using a peeling device of an RTR system including a winding-out section and winding sections for the long base material and the polyimide laminate, and the peeling is performed between the long base material and the polyimide laminate, and then the long base material is wound into a roll shape in the winding section for the long base material, and the polyimide laminate is wound into a roll shape in the winding section for the polyimide laminate.
In the polyimide laminate obtained as described above, one of the 1 st polyimide cured layer and the 2 nd polyimide cured layer is a polyimide base plate film, and the other is a carrier film, and in the subsequent step, the functional layer is formed on the polyimide base plate film, and the carrier film is separated to form the polyimide base plate film having the functional layer. That is, the carrier film may be formed to include the 1 st polyimide cured layer, and the polyimide substrate film may be formed to include the 2 nd polyimide cured layer, or the polyimide substrate film may be formed to include the 1 st polyimide cured layer, and the carrier film may be formed to include the 2 nd polyimide cured layer. From the viewpoint of preventing the surface smoothness of the polyimide substrate film from being affected by the surface smoothness of the conveying member, the former case (the carrier film is the 1 st cured polyimide layer, and the polyimide substrate film is the 2 nd cured polyimide layer) is preferable.
The thickness of the polyimide substrate film is preferably 1 to 50 μm, more preferably 1 to 20 μm, and still more preferably 1 to 15 μm, in view of maintaining the strength as a polyimide substrate and making it possible to manufacture a thin flexible device. If the thickness of the polyimide-based film exceeds 50 μm, the object may be lost when a thin flexible element is produced, and conversely, if it is less than 1 μm, the strength of the flexible element tends to be insufficient. The thickness of the carrier film is preferably 30 to 200 μm from the viewpoint of ensuring workability in forming the functional layer. If the thickness exceeds 200 μm, winding tends to be difficult, whereas if it is less than 30 μm, processing may be difficult. The applied 1 st solution and 2 nd solution may be adjusted to have these thicknesses.
The interlayer bond strength between the carrier film and the polyimide substrate film may be any that does not cause peeling between these layers when the functional layer is formed and allows peeling between these layers when the carrier film is separated after the functional layer is formed, and the interlayer bond strength is preferably 1N/m to 20N/m, more preferably 1.5N/m to 15N/m.
In the present invention, after the first solution 1 for forming the carrier film is applied to the carrier body to form at least the non-adhesive surface, the second solution 2 for forming the polyimide-based board film may be applied twice or more to form the polyimide-based board film having a plurality of polyimide layers. In this case, the heat treatment 2 may be divided into a plurality of times so that the heat treatment is performed at 60 to 300 ℃ every time the solution 2 is applied, and then the imidization is performed, or the solution 2 may be applied in a plurality of times, and the heat treatment is performed at 60 to 300 ℃ to form the non-stick state of the applied surface, and then the imidization is performed finally. In the former case, the polyimide substrate film may be separated individually for each polyimide layer, and in the latter case, a polyimide substrate film having a plurality of polyimide layers with different characteristics may be formed.
In addition, when the 1 st solution for forming the carrier film is applied to the carrier, the carrier film having a plurality of polyimide layers may be formed by applying the 1 st solution twice or more. In this case, the 1 st heat treatment may be performed every time the 1 st solution is applied to form a non-stick state, or the 1 st solution may be applied in a plurality of divided portions, and the 1 st heat treatment may be performed on the entire surface to form a non-stick surface on the outermost surface. In the former case, it is easy to individually provide the characteristics of the plurality of polyimide layers for each layer, and in the latter case, it is easy to integrally provide the characteristics for each layer. In addition, the production efficiency is high.
In the case of producing a flexible element of a bottom emission type such as an organic EL display device using the polyimide-based sheet film with a functional layer of the present invention, the flexible element is produced by a method described in Japanese Industrial Standards (JIS) J7375: the total light transmittance defined in 2008 is preferably 80% or more, and more preferably 85% or more. Similarly, when the flexible element is a touch panel, it is preferable that the polyimide substrate film having a thickness of 20 μm has a total light transmittance of 90% or more in consideration of visibility of a display and the like.
The difference (. DELTA.CTE) between the Coefficient of Thermal Expansion (CTE) of the polyimide substrate film and the CTE of the carrier film is preferably-25 ppm/K to 25ppm/K, more preferably-10 ppm/K to 10 ppm/K. When the difference in CTE is within these ranges, interlayer peeling or warpage between the transfer body and the polyimide laminate can be suitably suppressed in the process of obtaining the polyimide laminate, and also interlayer peeling or warpage can be suitably suppressed in the case of forming the functional layer on the polyimide substrate film.
The surface of the polyimide substrate film forming the interface with the carrier film preferably has an arithmetic mean roughness (Ra) of 0nm to 5nm, more preferably 0.3nm to 3nm, and still more preferably 0.3nm to 2 nm. In the present invention, since the 1 st cured polyimide layer and the 2 nd cured polyimide layer constituting the carrier film and the polyimide substrate film can be formed by a casting method, the flatness of the interface of these layers can be ensured. When the surface roughness of the polyimide substrate film forming the interface with the carrier film is within these ranges, the polyimide substrate film is not likely to be peeled off when the polyimide laminate is obtained or when the functional layer is formed, and the possibility of damage to the polyimide substrate film or the functional layer when the carrier film is separated can be reliably eliminated.
Similarly, the surface of the support film forming the interface with the polyimide substrate film is preferably 0 to 5nm in arithmetic mean roughness (Ra), more preferably 0.3 to 3nm, and still more preferably 0.3 to 2 nm. The surface of the carrier to which the first solution is applied is preferably 0 to 3.5nm in arithmetic mean roughness (Ra), more preferably 0.3 to 3nm, and still more preferably 0.3 to 2 nm. When the surface roughness of the carrier body to which the first solution is applied falls within these ranges, the possibility of unexpected peeling during the process of obtaining the polyimide laminate or damage when separating the carrier body from the polyimide laminate can be reliably eliminated. The arithmetic mean roughness (Ra) is a value obtained in accordance with JIS B0601: 2013, based on the measurement values measured by an Atomic Force Microscope (AFM).
In the present invention, the polyimide forming the carrier film is not particularly limited, but it is preferable to use at least one of pyromellitic dianhydride (abbreviated as PMDA) and 2, 3, 2 ', 3 ' -biphenyltetracarboxylic dianhydride (abbreviated as BPDA) or 3, 3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride (abbreviated as BTDA) as the acid anhydride compound, and 4,4 ' -diaminodiphenyl ether (4, 4 ' -diaminodiphenyl ether, abbreviated as 4,4 ' -DAPE) and 2, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl (2, 2 ' -dimethyl-4, 4 ' -diaminodiphenyl), for short: m-TB), or 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, abbreviated: BAPP) is preferably used. Among them, it is preferable that the acid anhydride compound is PMDA and the diamine compound is 4, 4' -DAPE.
In the present invention, the carrier film functions as a base when the functional layer is formed on the polyimide substrate film side, and can be removed after the production of the flexible element even if the workability and dimensional stability of the polyimide substrate film are sometimes ensured during the production of the functional layer. Therefore, the transparency may be poor. By using the polyimide laminate according to the present invention, a predetermined functional layer can be accurately and reliably formed on a polyimide substrate film, and a thin, lightweight, and flexible element can be obtained. That is, the carrier film may be separated and removed immediately after the functional layer is formed through various processes, or may be separated and removed after being integrated with the polyimide substrate film and bonded to another element member for a certain period of time. Further, as the element member, for example, there are: glass, plastic plate, film, circuit board, and frame.
On the other hand, regarding the polyimide forming the polyimide substrate film, in view of heat resistance or transparency of the polyimide substrate film as the functional layer to be provided, it is preferable to use, as the acid anhydride compound, any one of 4, 4' -oxydiphthalic anhydride (abbreviated as ODPA), pyromellitic dianhydride (PMDA), 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride (abbreviated as CBDA), 1, 2, 3, 4-cyclohexanetetracarboxylic dianhydride (1, 2, 3, 4-cyclohexanetetracarboxylic dianhydride) (abbreviated as CHDA), or 2, 2-bis (3, 4-anhydrodicarboxyphenyl) hexafluoropropane (2, 2-bis (3, 4-anhydrodicarboxyphenyl) hexafluoropropane FDA) (abbreviated as diamine) and 4, 6 or more, 4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl (4, 4 '-diamino-2, 2' -bis (trifluoromethylphenyl) biphenol, abbreviated as TFMB), 2 '-dimethyl-4, 4' -diaminobiphenyl (m-TB), or 4,4 '- (hexafluoroisopropylidene) diphenylamine (4, 4' - (hexafluoroisopropylidene) dianiline, abbreviated as 4, 46F). Among them, it is preferable that the acid anhydride compound is 6FDA, PMDA, or CBDA or more, and the diamine compound is TFMB or 4,46F or more.
Examples of the solvent for the polyimide precursor or the polyimide resin solution constituting the 1 st solution and the 2 nd solution include: n-methyl pyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc), Dimethylsulfoxide (DMSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol, halogenated phenols, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, carbonate esters (dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate, and the like), and the like.
The polyimide precursor solution or the polyimide solution may contain a release agent, if necessary. In addition, additives such as catalysts, antioxidants, heat stabilizers, antistatic agents, flame retardants, ultraviolet absorbers, lubricants, and the like may be contained.
As the functional layer formed on the polyimide-based plate film, a known device for securing the function of a flexible device can be used, and examples thereof include: organic EL/TFT, photoelectric conversion element, electronic paper driving element, color filter, touch panel, photoelectric conversion device, and the like. For example, when an organic EL display is manufactured as a flexible element, a TFT for image driving is used as a functional layer. The material of the TFT is silicon semiconductor or oxide semiconductor. In the case of a conventional technique without using a flexible substrate, a barrier layer of an inorganic component is provided on a hard support such as plate glass, and a TFT is formed thereon. This formation requires a high-temperature treatment (about 300 ℃ to about 400 ℃), but polyimide can withstand the high-temperature treatment. In the case of manufacturing a touch panel as a flexible element, the functional layer may be an electrode layer such as a transparent conductive film or a metal mesh. Examples of the transparent conductive film include: ITO (tin-doped Oxide), SnO, ZnO, and Indium-Zinc Oxide (IZO). When these electrode layers are formed, a conductive layer having a small resistance value can be formed by performing heat treatment at 200 ℃ or higher, but polyimide can withstand such high-temperature treatment. In addition, the transparent conductive film is not limited to the touch panel, and is also referred to as a "transparent conductive layer" when the transparent conductive film is used as a functional layer.
As a preferred embodiment when forming the functional layer on the polyimide substrate film of the polyimide laminate, as described above, it is preferable to form the functional layer continuously on the polyimide substrate film while winding up the polyimide laminate after the long polyimide laminate is temporarily wound up on the winding roll. Further, the polyimide laminate may be cut into sheets of a predetermined length while the wound polyimide laminate is wound out, and the functional layer may be formed on the polyimide sheet film for each sheet of the polyimide laminate.
After forming a functional layer on the polyimide substrate film, the carrier film of the polyimide laminate is separated to obtain a polyimide substrate film having a functional layer. Here, the method for separating the carrier film is not particularly limited, and a known method can be used. In this case, the carrier film may be peeled by a mechanical means such as a pinching point tool such as a pincer for forming a peeling start point portion, a suction plate, or air blowing of the peeling portion formed immediately after the peeling start point portion. For example, the end portion of the carrier film is pinched with a pincer to peel off the carrier film, and the polyimide substrate film having the functional layer is completely separated using another tool (pincer, bar, blade, sheet, or the like) with the peeled portion as a starting point. Alternatively, instead of the above-mentioned forceps, needle-like, hook-claw-like, or insect-foot-like tools may be used, and these tools may be inserted into the interface between the carrier film and the polyimide substrate film with the functional layer to peel off the end portion of the carrier film, or the polyimide substrate film with the functional layer may be sucked by a suction plate to peel off the carrier film. The method using the suction plate as described above can be referred to as a preferable method in terms of enabling the polyimide substrate film with the functional layer to be stably held and conveyed simultaneously with peeling. The suction plate may be planar or may be curved such as a semicircle. Further, after the end portion of the carrier film is peeled off by any of the methods described above, the carrier film may be peeled off by a suction plate or by blowing compressed air.
Here, a case where a touch panel is manufactured using the long polyimide laminate of the present invention will be described as an example. In this example, an RTR-type continuous production apparatus shown in fig. 4 is used, and the continuous production apparatus includes: a wind-out roll (wind-out section) 13 for winding out the long polyimide laminate 8 wound in a roll shape, a conveying roll (guide roll) 14, a process treatment section 15, and a wind-up roll (wind-up section) 17. The polyimide laminate 8 wound out from the wind-out roll 13 is subjected to a process treatment section 15 via a conveyance roll 14 for preventing wrinkles or winding displacement, and ITO is deposited as a functional layer on the surface of the polyimide laminate on the polyimide substrate film side at 100 to 400 ℃. Thereafter, the polyimide laminate 16 with the functional layer is wound into a roll shape by a winding roll 17 via the conveying roll 14.
Instead of depositing ITO by the process treatment unit 15, ITO may be provided on a resin film support made of polyethylene terephthalate, polyethylene, or the like, and the ITO surface may be brought into close contact with the surface of the polyimide substrate film in the polyimide laminate, and thereafter, the resin film support may be peeled off to form ITO on the polyimide laminate.
Next, the polyimide laminate 16 with the functional layer wound in a roll shape is wound out and cut into a sheet shape with a predetermined length. The size of the sheet may be arbitrarily determined according to the size of the touch screen to be manufactured. The ITO in the polyimide laminate with functional layers cut into a sheet shape was processed into a shape of a circuit used as a touch panel by etching. The etching may use a well-known method. For example, a liquid or film-like photoresist (either negative or positive) is laminated on the surface of ITO. In the case of a liquid photoresist, the solvent may be evaporated and dried by heat treatment after lamination. Then, a well-known photomask patterned into a circuit shape is stacked on the photoresist, exposed to light by a well-known exposure machine, and developed by a well-known developer. The developing solution may be appropriately selected from an alkaline aqueous solution, an organic solvent, and the like according to the photoresist used. By the development, a photoresist conforming to the shape of a circuit used as a touch panel remains on the surface of the ITO. Then, the ITO layer is exposed to an etching solution to remove the ITO layer in the portion where the photoresist layer is not laminated. As the etching solution, a known etching solution can be used, and examples thereof include an iron chloride-based etching solution and a copper chloride-based etching solution. Then, the remaining photoresist was stripped and washed with water. Further, the carrier film is peeled off with a nipper or the like, thereby obtaining an ITO-equipped polyimide substrate film used as a touch panel.
In the process processing unit 15 of the continuous manufacturing apparatus shown in fig. 4, after ITO is formed on the polyimide laminate, the polyimide laminate is processed into a shape of a circuit used as a touch panel by etching, the polyimide laminate with the functional layer is wound around a winding roller 17, and then, similarly to the above, the polyimide laminate with the ITO used as a touch panel is cut into a sheet shape with an arbitrary size according to the size of the touch panel to be manufactured, and the carrier film is peeled off to obtain the polyimide laminate film with ITO used as a touch panel.
As another embodiment of manufacturing a touch panel using the long polyimide laminate of the present invention, a functional layer may be formed by laminating silver or copper nanowires (hereinafter referred to as "nanowires") using a well-known uv-curable adhesive instead of ITO. In this case, in the process treatment section 15 of the RTR-type continuous manufacturing apparatus, an ultraviolet curable resin is applied to the surface of the polyimide substrate film side of the polyimide laminate, and the resultant is dried to laminate the nanowire into a circuit shape. In the case of stacking, a groove may be provided in the shape of the circuit, and the nanowire may be provided in the groove. Then, the ultraviolet-curable adhesive is cured by irradiation with ultraviolet light, the nanowires are bonded to the polyimide laminate, and the polyimide laminate 16 with the functional layer is wound into a roll shape by a winding roll 17. Then, the polyimide laminate with functional layer 16 was cut into a sheet with an arbitrary length and the carrier film was peeled off, as in the case of the previous production example, while being rolled out, to obtain a polyimide substrate film with nanowires to be used as a touch panel. In this case, the end face of the nanowire may be smoothed by polishing or the like.
In the present invention, the long polyimide laminate may be cut into a sheet shape in advance according to the size of the flexible element such as a touch panel to be manufactured, ITO may be formed on the sheet-shaped polyimide laminate, the sheet-shaped polyimide laminate may be processed into a shape of a circuit to be used as a touch panel by etching, and the carrier film may be peeled off to obtain an ITO-equipped polyimide substrate film to be used as a touch panel or the like.
On the other hand, the case of producing a coverlay using the long polyimide laminate of the present invention will be described below as an example. Similarly to the case of manufacturing a touch panel, using an RTR-type continuous manufacturing apparatus as shown in fig. 4, the polyimide laminate 8 wound from the winding-out roll 13 is passed through the conveying roll 14, and an adhesive layer is formed as a functional layer on the surface of the polyimide laminate on the polyimide substrate film side in the process treatment section 15. As a method for forming the adhesive layer, a known resin material such as an epoxy resin, an acrylic resin, a polyimide resin, or a silicone resin, which is a raw material of the adhesive layer, or a known adhesive (pressure-sensitive adhesive) such as a solvent-based adhesive, a latex-based adhesive, a hot-melt adhesive, or a rubber-based adhesive is applied using an application device such as a lip coater, and dried. Then, the polyimide laminate with an adhesive layer was wound into a roll shape by a winding roll 17, and then cut into a sheet shape with an arbitrary size according to the size of the produced cover film, and the carrier film was peeled off to obtain a polyimide laminate film with an adhesive layer used as a cover film. When the adhesive layer is formed using the adhesive, the adhesive layer may be referred to as an "adhesive layer". In the case where the adhesive layer is used as the functional layer of the present invention, the cover layer may be bonded to the polyimide laminate after ITO is formed thereon and further when the cover layer is laminated thereon in the case of manufacturing the touch panel.
In the present invention, in the process of obtaining a polyimide substrate film with a functional layer such as the polyimide substrate film provided with an adhesive layer, a long polyimide substrate film with a functional layer may be wound by separately providing a winding roll for winding a carrier film in the continuous manufacturing apparatus of the RTR system as described above. That is, in the process processing section, after the functional layer is formed on the polyimide laminate, the carrier film is peeled off in the continuous manufacturing apparatus of the RTR system, and the carrier film is wound by a winding roll (not shown) for the carrier film, and the polyimide substrate film with the functional layer is wound by a winding roll 17. The wound polyimide-based sheet film with the functional layer may be cut into a sheet shape according to the size of the flexible element, if necessary.
Further, in the case of manufacturing an organic EL display using the long polyimide laminate of the present invention, for example, a polyimide laminate is cut into a sheet shape in advance according to the size of the organic EL display to be manufactured, and a glass sheet is laminated on the surface of the sheet-shaped polyimide laminate on the side of the carrier film. Then, a TFT, an electrode layer, a light-emitting layer, and an electrode layer are sequentially formed as functional layers on the surface on the polyimide substrate film side, the functional layers are hermetically sealed with a glass substrate, a multilayer thin film, or the like, and the glass sheet and the carrier film are peeled off, thereby obtaining a polyimide substrate film with functional layers which can be used as an organic EL display. Incidentally, the formation temperature when forming the TFT is 300 ℃ to 500 ℃.
In the case of manufacturing a liquid crystal display device using the long polyimide laminate of the present invention, a known color filter resist ink containing a vinyl ester resin, a phenol resin, an acrylic resin, or the like as a base resin may be mounted as a color filter resist layer.
In the case of producing the various flexible elements using the long polyimide laminate of the present invention, the following functional layers may be mounted in order to improve the respective characteristics. That is, in order to improve the abrasion resistance of the polyimide-based plate film, a known compound such as a melamine resin, a urethane resin, an acrylic resin, a silicon resin, a silane compound, a metal oxide, or the like may be mounted as a hard coat layer. In addition, a known gas barrier layer such as alumina or silica may be mounted to suppress the permeation of oxygen or water vapor through the polyimide substrate film. In addition, in order to control optical characteristics, dimensional stability, and the like of the polyimide-based sheet film, a known transparent resin such as a cyclic olefin resin or an ester resin may be mounted as a transparent resin layer.
In addition to the functional layers, well-known wiring materials such as copper, silver, gold, titanium, tungsten, and ITO may be mounted as wiring layers for the purpose of transmission and reception of electronic signals between flexible elements, between flexible element and output device, or between flexible element and input device.
As described above, the polyimide-based plate film with a functional layer obtained by the present invention has excellent smoothness and little contamination with foreign substances. Further, since the film is thin and excellent in light transmittance, the film is extremely suitable for obtaining a vapor deposition mask, a Fan-out Wafer Level Package (FOWLP) substrate, and the like, in addition to various flexible elements such as a touch panel including a flexible display such as an organic EL, electronic paper, and a solar cell.
[ examples ]
The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these.
<1. methods for measuring various physical Properties and testing Properties >
[ measurement of peeling Strength ]
The peel strength between the carrier and the carrier film and between the carrier film and the polyimide substrate film were measured by processing these laminates into a long strip having a width of 1mm to 10mm and a length of 10mm to 25mm, and peeling off the carrier film in a 180 ° direction using a tensile tester (strolograph) -M1 manufactured by toyo seiki co. Further, the peel strength is strong and peeling is difficult, and it is assumed that peeling is "impossible".
[ transmittance ]
The polyamide substrate film was cut into 5cm squares, and the total light transmittance was measured using a HAZE METER (HAZE METER) NDH-5000 manufactured by Nippon Denshoku industries.
[ surface roughness Ra ]
The surface roughness Ra of the carrier, carrier film, and polyimide substrate film was cut to 3Gm square, and measured using AFM manufactured by Bruker (Bruker) AXS for surface roughness Ra (JIS B0601: 2013).
[CTE]
The CTE of the carrier, carrier film, and polyimide film was cut into 3 mm. times.15 mm squares, and a tensile test was performed at a temperature of 30 ℃ to 260 ℃ at a constant temperature rise rate (10 ℃ C./min) while applying a load of 5.0g to one side of each of them using a Thermal Mechanical Analysis (TMA) apparatus manufactured by a Seiko Instrument, and the CTE (. times.10) was measured from the elongation of the polyimide film with respect to the temperature-6/K)。
<2. Synthesis of Polyamic acid (polyimide precursor) solution >
The following are the raw materials, aromatic diamino compounds, anhydrides of aromatic tetracarboxylic acids, and solvents used in the synthesis of polyamic acid (polyimide precursor) solutions used in the following synthesis examples or examples and comparative examples.
[ aromatic diamino Compound ]
4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl (TFMB)
4,4 '-diaminodiphenyl ether (4, 4' -DAPE)
[ acid anhydride of aromatic tetracarboxylic acid ]
Pyromellitic dianhydride (PMDA)
2, 2-bis (3, 4-anhydrodicarboxyphenyl) hexafluoropropane (6FDA)
[ solvent ]
N, N-Dimethylacetamide (DMAc)
(Synthesis example 1)
TFMB (9.4g) was added to 127.5g of the solvent DMAc while stirring in a 300ml separable flask under a nitrogen stream, and the mixture was heated and dissolved at 50 ℃. Then, 6FDA (13.09g) was added. Thereafter, the solution was continuously stirred at room temperature for 3 hours to effect polymerization, thereby obtaining 200g of a pale viscous polyamic acid A varnish. The polyamic acid A varnish was cured under heating conditions described later to obtain a polyimide resin A (CTE: 70 ppm/K).
(Synthesis example 2)
4, 4' -DAPE (10.753g) was added to 170g of DMAc as a solvent while stirring in a 300ml separable flask under a nitrogen stream, and the mixture was heated and dissolved at 50 ℃. Then, PMDA (11.747g) was added. Thereafter, the solution was continuously stirred at room temperature for 3 hours to effect polymerization, thereby obtaining 200g of a pale viscous polyamic acid B varnish. The polyamic acid B varnish was cured under heating conditions described later to obtain a polyimide resin B (CTE: 69 ppm/K).
<3. formation of PI layer by coating >
The following materials used in the following examples and comparative examples are shown.
Long base material (carrier)
Polyimide film (yupexix (UPILEX) S manufactured by yolking gmbh of yu), thickness of 0.75mm, CTE: 18 ppm/K.
A polyimide film (Kapton)300H manufactured by tokyo corporation), a thickness of 75 μm, a CTE: 27 ppm/K.
(example 1)
The long base material 2 was a clean eupezil (UPILEX) S (508 mm in width × 1100m in length × 0.75mm in thickness) wound in a roll, and the polyamic acid varnish B applied from the mohno pump 4 was applied to the long base material at a film thickness of 500 μm while being wound at a speed of 8m/min by a roll-to-roll coating and drying and curing apparatus of a roll-to-roll system including a winding-out section 1, a lip coater (not shown), heat treatment apparatuses (1 st heat treatment apparatus 5, 2 nd heat treatment apparatus 7) including a continuous drying furnace and a continuous furnace, and a winding section 9 and a winding section 10 for a carrier and a polyimide laminate, as shown in fig. 1. The polyimide (cured polyimide layer) B was formed by passing the sample through a continuous drying furnace (heat treatment apparatus 15) including a plurality of furnaces to dry the sample at 90 ℃ for 2 minutes and at 130 ℃ for 1 minute, and further passing the sample through a continuous furnace (heat treatment apparatus 1) including a plurality of furnaces in which the temperature gradually increases from the furnace on the sample inlet side to the furnace on the sample outlet side, and gradually heating the sample for 20 minutes from 130 ℃ to 400 ℃.
Next, the polyamic acid a varnish was applied from the mohno pump 6, and the polyamic acid a varnish was applied to the polyimide B so that the film thickness became 150 μm, and the resultant was dried at 90 ℃ for 2 minutes and at 130 ℃ for 1 minute in a continuous drying furnace (heat treatment apparatus 2) including a plurality of furnaces, and further heated stepwise from 130 ℃ to 400 ℃ for 10 minutes in total in a continuous furnace (heat treatment apparatus 2) including a plurality of furnaces in which the temperature was increased stepwise from the furnace on the sample inlet side to the furnace on the sample outlet side, to form a polyimide (cured polyimide layer) a. Then, the roll-shaped polyimide laminate of example 1 was obtained by winding the laminate 8 of the polyimide B and the polyimide a in the winding section 10 while peeling off the yupex (UPILEX) S as the long base material 2.
Regarding the thickness of each layer of the polyimide laminate 8 obtained, the thickness of the polyimide B was 50 μm and the thickness of the polyimide a was 15 μm. Further, the peel strength between the Unix (UPILEX) S (long base material) -polyimide B was 0.12N/m, and the peel strength between the polyimide B-polyimide A was 0.10N/m, and both could be easily peeled off. On the other hand, the surface roughness Ra of the peeled polyimide a was 1.0nm, the surface roughness Ra of the peeled polyimide B was 1.0nm, and the surface roughness Ra of eumerix (UPILEX) S was 1.15 nm. Further, the light transmittance of the polyimide a was 91%.
Next, the polyimide laminate 8 in a roll form obtained as described above was subjected to roll-to-roll continuous manufacturing equipment including a unwinding section 13, a conveying roll 14, a processing section 15, and a winding section 17 as shown in fig. 4, and functional layers were formed as described below. That is, the polyimide laminate 8 was transported at a speed of 5m/min, and while being wound out in the longitudinal direction so that the polyimide a surface of the polyimide film became the upper surface, it was introduced into a process treatment section 15 provided in a vacuum chamber via a transport roller 14, and the polyimide a surface was continuously treated by a sputtering method in the process treatment section 15 to form ITO having a film thickness of 50 nm. Then, the polyimide laminate 16 with a functional layer, which is provided with ITO, is wound in a roll shape by the winding unit 17.
The polyimide laminate 16 with a functional layer obtained as described above was cut into a sheet of 370mm × 450mm while being wound, and ITO obtained as a film was subjected to XY transparent circuit processing. At this time, no circuit is formed at the intersection of the Y circuit and the X circuit.
Then, an overcoat layer was applied to the intersection between the Y circuit and the X circuit, heat treatment was performed at 250 ℃ to cure the overcoat layer, bridge processing was performed across the overcoat layer using silver paste to complete the XY circuit, further, the overcoat layer was applied again to the entire surface on the ITO film side, annealing was performed at 270 ℃, and curing of the overcoat layer and crystallization of ITO were performed.
Then, an optical clear Tape (OCA) was attached to the surface of the overcoated layer that was coated again, 8146-2 manufactured by 3M company, and a cover glass was attached thereto. Thereafter, the polyimide B as a carrier film was mechanically peeled off, thereby completing a touch panel substrate having flexibility.
Comparative example 1
The roll-to-roll coating, drying and curing apparatus shown in fig. 1 was used to coat the polyamic acid a varnish so as to have a film thickness of 150 μm by winding the clean Kapton (Kapton)300H (520 mm in width × 1100m in length × 75 μm in thickness, and surface roughness Ra of 4.0nm) wound into a roll at a speed of 8m/min from the mohno pump 4, and passed through a continuous drying furnace including a plurality of furnaces to dry at 90 ℃ for 2 minutes and at 130 ℃ for 1 minute, and further passed through a continuous furnace including a plurality of furnaces in which the temperature gradually increases from the furnace on the sample inlet side to the furnace on the sample outlet side, and heated stepwise from 130 ℃ to 400 ℃ for 10 minutes in total to form polyimide a having a thickness of 15 μm. Then, a laminate of Kapton (Kapton)300H and polyimide a was wound to obtain a polyimide laminate in a roll shape of comparative example 1.
Here, the polyimide a was not peeled off from Kapton (Kapton)300H in the roll-shaped polyimide laminate obtained, and thus the functional layer was not formed. The surface roughness Ra of the exposed surface of the polyimide A was 1.0 nm.

Claims (20)

1. A method for manufacturing a polyimide-based plate film with a functional layer is characterized in that:
a method for producing a long polyimide laminate comprising a 1 st polyimide cured layer composed of a 1 st solution and a 2 nd polyimide cured layer composed of a 2 nd solution, which are separated from a carrier with the traveling direction of the carrier being the longitudinal direction, is provided by applying the 1 st solution containing a polyimide precursor or a polyimide resin solution on the carrier continuously supplied to perform a 1 st heat treatment to form an unbonded surface on at least the surface of the 1 st solution, and applying the 2 nd solution containing a polyimide precursor or a polyimide resin solution to perform a 2 nd heat treatment to obtain a long polyimide laminate,
and setting one of the 1 st polyimide hardened layer and the 2 nd polyimide hardened layer of the long polyimide laminate as a polyimide base plate film, and setting the other as a carrier film, and after a functional layer is formed on the polyimide base plate film, separating the carrier film to obtain the polyimide base plate film having the functional layer.
2. The method for producing a polyimide-based plate film with a functional layer according to claim 1, wherein,
the method for manufacturing a polyimide laminate includes the steps of winding the long polyimide laminate around a winding roll, continuously forming the functional layer on the polyimide laminate film while winding out the polyimide laminate, or cutting the polyimide laminate into sheets having a predetermined length while winding out the polyimide laminate, and forming the functional layer on the polyimide laminate film for each sheet of the polyimide laminate.
3. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the carrier body is separated before the 2 nd heat treatment is performed or after the 2 nd heat treatment is performed in the process of obtaining the long polyimide laminate.
4. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the carrier is a metal roll, an endless belt, or a long base material wound in a roll shape.
5. The method for producing a polyimide-based board film with a functional layer according to claim 1 or 2, wherein the carrier film contains the 1 st cured polyimide layer, and the polyimide-based board film contains the 2 nd cured polyimide layer.
6. The method for manufacturing a polyimide-based board film with a functional layer according to claim 1 or 2, wherein the polyimide-based board film includes the 1 st cured polyimide layer, and the carrier film includes the 2 nd cured polyimide layer.
7. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the 1 st solution containing the polyimide resin solution is applied to the carrier, and the 1 st heat treatment is performed at a maximum temperature of 60 ℃ to 300 ℃, whereby the non-adhesive surface is formed on the surface of the 1 st solution.
8. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the 1 st solution containing the polyimide precursor is applied to the carrier and a 1 st heat treatment is performed at a maximum temperature of 100 ℃ to 450 ℃, thereby forming the 1 st cured polyimide layer from the 1 st solution.
9. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the maximum temperature of the heat treatment in the 2 nd heat treatment is 100 ℃ to 450 ℃.
10. The method for producing a polyimide substrate film with a functional layer according to claim 1 or 2, wherein the interlayer adhesion strength between the 1 st cured polyimide layer and the 2 nd cured polyimide layer is 1 to 20N/m, and the thickness of the 1 st cured polyimide layer or the 2 nd cured polyimide layer as the polyimide substrate film is 1 to 50 μm.
11. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the 1 st cured polyimide layer or the 2 nd cured polyimide layer as the polyimide-based plate film has a total light transmittance of 80% or more.
12. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the carrier comprises a long base material wound in a roll shape, and the long base material is a polyimide film, a SUS foil, a copper foil, or a composite of two or more of these laminated layers.
13. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the 1 st polyimide cured layer is formed by coating two or more kinds of the 1 st solutions containing the polyimide precursor or the polyimide resin solution by overlapping application.
14. The method for producing a polyimide-based plate film with a functional layer according to claim 1 or 2, wherein the 2 nd cured polyimide layer is formed by coating two or more of the 2 nd solutions containing the polyimide precursor or the polyimide resin solution by overlapping application.
15. A long polyimide laminate with a functional layer, characterized in that: with respect to the longitudinal direction of a long polyimide laminate in which a carrier film and a polyimide substrate film are laminated, a functional layer is continuously formed on the polyimide substrate film, the carrier film includes a polyimide hardened layer obtained by hardening one of a 1 st solution or a 2 nd solution containing a polyimide precursor or a polyimide resin solution, the polyimide base plate film includes the polyimide hardened layer formed by hardening the other of the 1 st solution or the 2 nd solution including the polyimide precursor or the polyimide resin solution, and has a thickness of 1 to 50 μm, and has a total light transmittance of 80% or more, and has a surface roughness with an arithmetic average roughness Ra of 0nm to 5nm at an interface with the carrier film, the interlayer bonding strength of the carrier film and the polyimide base plate film is 1N/m-20N/m.
16. The long polyimide laminate with functional layers according to claim 15, wherein the functional layers are indium tin oxide films.
17. The long polyimide laminate with functional layers according to claim 15, wherein the functional layers are thin film transistors.
18. The long polyimide laminate with functional layers according to claim 15, wherein the functional layers are layers containing any one or a combination of two or more selected from the group consisting of a transparent conductive layer, a wiring layer, a conductive layer, a gas barrier layer, a thin film transistor, an electrode layer, a light-emitting layer, an adhesive layer, a transparent resin layer, a color filter resist, and a hard coat layer.
19. A long polyimide laminate which is a long polyimide laminate in which a carrier film and a polyimide substrate film are laminated, the carrier film including a polyimide cured layer which is cured from one of a 1 st solution or a 2 nd solution containing a polyimide precursor or a polyimide resin solution, the polyimide substrate film including the polyimide cured layer which is cured from the other of the 1 st solution or the 2 nd solution containing the polyimide precursor or the polyimide resin solution, the long polyimide laminate being characterized in that: the interlayer bonding strength between the carrier film and the polyimide-based plate film is 1N/m-20N/m, the thickness of the polyimide-based plate film is 1 mu m-50 mu m, and the total light transmittance is more than 80%.
20. The utility model provides a take long polyimide base plate membrane of functional layer which characterized in that: a functional layer is continuously formed in the longitudinal direction of a long polyimide-based plate film including a polyimide cured layer formed by curing a solution containing a polyimide precursor or a polyimide resin solution, wherein the long polyimide-based plate film has a thickness of 1 to 50 [ mu ] m, a total light transmittance at a thickness of 20 [ mu ] m of 80% or more, and a surface opposite to the functional layer has a surface roughness with an arithmetic mean roughness Ra of 0 to 5 nm.
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