CN104952780B - Method for manufacturing flexible element, and flexible element manufacturing apparatus - Google Patents
Method for manufacturing flexible element, and flexible element manufacturing apparatus Download PDFInfo
- Publication number
- CN104952780B CN104952780B CN201510148729.8A CN201510148729A CN104952780B CN 104952780 B CN104952780 B CN 104952780B CN 201510148729 A CN201510148729 A CN 201510148729A CN 104952780 B CN104952780 B CN 104952780B
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- Prior art keywords
- flexible substrate
- flexible
- manufacturing
- hard support
- flexible element
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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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
- H01L27/1259—Multistep manufacturing methods
- H01L27/1262—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate
- H01L27/1266—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate the substrate on which the devices are formed not being the final device substrate, e.g. using a temporary substrate
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Abstract
The invention provides a method for manufacturing a flexible element, a flexible element and a flexible element manufacturing device, which are simple and low in manufacturing cost, can be applied to various resins, and can easily remove a hard support from a flexible substrate with a functional layer. The method for manufacturing a flexible element of the present invention includes the steps of: a flexible substrate forming step of forming a flexible substrate on a hard support by applying a resin solution on the hard support; a functional layer forming step of forming a functional layer on the flexible substrate; and a support removing step of removing the flexible substrate on which the functional layer is formed from the hard support together with the functional layer, wherein the method for manufacturing a flexible element comprises: in the flexible substrate forming step, the hard support is subjected to a heat treatment and then coated with a resin solution.
Description
Technical Field
The present invention relates to a method for manufacturing a flexible device in which a hard support is easily removed from a flexible substrate having a functional layer formed thereon, a flexible device manufactured by the manufacturing method, and a flexible device manufacturing apparatus for the manufacturing method.
Background
Electronic components such as liquid crystal displays, organic Electroluminescence (EL) displays, solar cells, touch panels (touch panels), and color filters (color filters) are mainly manufactured using glass as a substrate. An electronic component using a flexible substrate such as plastic instead of the glass substrate is called a so-called flexible component. In the case of manufacturing a flexible display which is one type of flexible element, in order to suppress an increase in manufacturing cost due to introduction of a novel device, it is desirable to flexibly use a conventional manufacturing technique for a glass substrate (including a manufacturing apparatus).
An example of a method for manufacturing a flexible display using a conventional manufacturing technique is as follows: first, a flexible substrate is mounted on a glass support, and further, a functional element is mounted on the flexible substrate, and a conductive pattern is formed and sealed (hereinafter collectively referred to as "functional layer forming step"). Then, the flexible substrate is peeled off from the support together with the functional element (hereinafter referred to as "support removing step"). Therefore, it is important that the glass base material and the flexible substrate are not peeled off in the functional layer forming step, and that the flexible substrate is peeled off without damaging the flexible substrate itself and the functional device (dam) in the support removing step.
In the manufacturing process of the flexible element, the flexible substrate is usually subjected to a heat treatment (200 to 500 ℃) and various chemical treatments. Therefore, the flexible substrate is required to have heat resistance and chemical resistance. Polyimide resins have been studied as materials for flexible substrates that meet such demands (see patent documents 1 to 3). The polyimide resin has the following characteristics: since the Coefficient of linear thermal expansion (CTE) is low and the control thereof is relatively easy, it is difficult to cause a problem in a manufacturing process and a use of a product, which are exposed to a high temperature.
Among them, patent document 1 discloses a method for manufacturing a flexible element, which includes the steps of: patent document 1 discloses a method of peeling a carrier substrate from a resin film by applying a liquid resin composition onto the carrier substrate to form a solid resin film, forming a circuit on the resin film, and: the resin film has excellent releasability from a carrier substrate and does not cause defects such as peeling of the circuit. However, there is no disclosure about controlling the peel strength between the carrier substrate and the resin film. That is, the difficulty of peeling the carrier substrate-resin film in the functional layer forming step is not clear.
Further, patent document 2 discloses the following process (process): a film element is obtained by forming a polyimide film on a support and further forming a thin film element thereon and then peeling the film element from the support, and the film element is disclosed in the following: the peeling force from the polyimide film on the support is 0.05N/cm to 1.5N/cm. And discloses that: in this case, the membrane element is not peeled off during the processing, and can be quickly peeled off after the processing. However, the resin applicable in the process is limited to a resin having an indole (benzazole) skeleton.
Further, patent document 3 discloses the following method: after a layer to be peeled is formed by providing a nitride layer on a substrate and further providing an oxide layer thereon, and an insulating layer and an element are formed thereon, the layer or the interface of the oxide layer is peeled by a physical method. However, since the layer to be peeled as described above needs to be provided on the substrate, the production process is complicated, and the production cost is increased.
As described above, means that can be performed easily at low cost without peeling the flexible substrate from the support when the functional layer is formed and without damaging the flexible substrate and the functional layer when the flexible substrate is peeled from the support thereafter is desired.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent application laid-open No. 2010-202729
[ patent document 2] Japanese patent laid-open No. 2012-140560
[ patent document 3] Japanese patent laid-open No. 2003-174153
Disclosure of Invention
[ problems to be solved by the invention ]
The following methods are considered advantageous from the viewpoints of forming various functional layers with good precision and excellent workability in production: as described above, a flexible substrate is formed on a rigid support such as a glass substrate in advance, a functional layer is provided in a state where the flexible substrate is fixed to the rigid support, and the flexible substrate is separated from the rigid support to manufacture a flexible device. However, the flexible element cannot be separated well when separated from the rigid support, and the flexible substrate may be broken, thereby causing various troubles (crank) such as an influence on the functional layer. In addition, the methods known so far are not sufficient from the viewpoint of suppressing the production cost to a low level and being applicable to various resins, and further improvement is required.
Accordingly, an object of the present invention is to provide a method for manufacturing a flexible element, which is simple and inexpensive to manufacture, has so-called general applicability to various resins, and is easy to remove a hard support from a flexible substrate having a functional layer formed thereon.
[ means for solving problems ]
That is, the present invention is a method for manufacturing a flexible element, including the steps of: a flexible substrate forming step of forming a flexible substrate on a hard support by applying a resin solution on the hard support; a functional layer forming step of forming a functional layer on the flexible substrate; and a support removing step of removing the flexible substrate having the functional layer formed thereon from the rigid support together with the functional layer, wherein the method for manufacturing a flexible element comprises: in the flexible substrate forming step, the hard support is subjected to a heat treatment and then coated with a resin solution.
In the present invention, the maximum temperature of the heat treatment is preferably 300 ℃ or higher, and more preferably 360 ℃ or higher.
In the present invention, it is preferable that the resin solution is applied to the hard support within 180 minutes after the heat treatment is completed.
In addition, the present invention is a flexible element manufactured by the manufacturing method of the flexible element. In particular, it is preferred that the flexible element is a touch screen.
Further, the present invention is a flexible element manufacturing apparatus for a flexible element manufacturing method, wherein: the apparatus comprises a means for continuously heat-treating the hard support at 300 ℃ or higher, preferably 360 ℃ or higher.
In addition, the present invention is a resin solution for forming the flexible substrate of the flexible element.
[ Effect of the invention ]
The method for manufacturing a flexible element of the present invention can be applied to a flexible element by applying various resins without adding a complicated step such as adding a release layer, and therefore, an increase in manufacturing cost due to introduction of a novel device can be suppressed, and a conventional manufacturing technique for a glass substrate can be flexibly used. Therefore, replacement of electronic elements such as liquid crystal displays, organic EL displays, solar cells, touch panels, and color filters from glass substrates to flexible substrates is promoted.
Drawings
Fig. 1 is a schematic explanatory view showing a flexible member manufacturing apparatus of the present invention.
[ description of symbols ]
10: flexible substrate manufacturing apparatus
11: hard support
12: flexible substrate
13: no. 1 continuous heat treatment apparatus
14: resin solution supply device
15: 2 nd continuous heat treatment apparatus
16: conveying belt
Detailed Description
Hereinafter, one embodiment of the method for manufacturing a flexible element of the present invention will be described in detail.
The method for manufacturing a flexible element according to the present invention is a method for manufacturing a flexible element having a functional layer having a predetermined function on a flexible substrate, and includes the following 3 steps.
(1) A flexible substrate forming step of applying a resin solution to a hard support to form a flexible substrate on the hard support
(2) A functional layer forming step of forming a functional layer on the flexible substrate
(3) Each step of the support removing step of removing the hard support from the flexible substrate having the functional layer formed thereon
Therefore, in the present invention, in the flexible substrate forming step, the hard support is subjected to a heat treatment and then coated with the resin solution.
First, a flexible substrate forming process will be described.
The hard support is not limited in its kind as long as it is an inorganic substance and can secure the performance as a laminate, and examples thereof include glass, ceramics, and metals. Here, the metal may be one or two or more metal materials selected from the group consisting of copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, silicon, bismuth, indium, or an alloy of these metals, and may be combined with glass to form a hard support. Examples of the ceramics include alumina, silica, and silicon wafer. More preferred is glass having excellent suitability for a conventional process for producing a flexible element.
In addition, in order to adjust the surface properties and improve the adhesion to the flexible substrate, the following treatments may be applied to the surface of these hard supports: chemical surface treatments such as sizing (sizing), chrome plating, nickel plating, chrome-nickel plating, copper-zinc alloy plating, copper oxide precipitation or aluminum alcoholate, aluminum chelate, silane coupling agent, titanate coupling agent, titanium compound such as titanium alkoxide, silane compound such as alkoxysilane, triazine thiol, benzotriazole, acetylene alcohol, acetophenones, catechol, o-quinone, tannic acid, and hydroxyquinoline, and mechanical surface treatments such as surface roughening treatment.
A resin solution is applied to the hard support to form a flexible substrate on the hard support. The resin solution is obtained by dissolving a known resin in a known solvent. Examples of the resin include: polybenzoxazole, polyamideimide, polyimide, or polyimide precursor. Polyimide or a polyimide precursor excellent in heat resistance and chemical resistance when a flexible substrate is produced is preferable. Examples of the solvent include: n-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol, halogenated phenol, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether systems, triethylene glycol dimethyl ether systems, carbonate systems (dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate, and the like), and the like.
In the case where the resin is polyimide or a polyimide precursor, a resin solution containing polyimide or a polyimide precursor is applied to a hard support, and the hard support is subjected to a heat treatment to harden the resin solution, thereby producing a flexible substrate. In this case, the layer of the resin solution before curing is referred to as a "pre-polyimide resin layer".
In the case where the flexible substrate is formed of polyimide, the structure of polyimide is applicable without particular limitation, and polyimide having an alicyclic structure in the main chain skeleton (hereinafter referred to as "alicyclic-containing polyimide") or polyimide having a fluorine atom (hereinafter referred to as "fluorine-containing polyimide") is preferable in terms of easy removal from the rigid support. Examples of alicyclic group-containing polyimides are: a compound containing at least one or more alicyclic structure-containing diamino compounds such as 9, 9-bis (4-aminophenyl) fluorene (DCHM) and Cyclohexylamine (CHA) and alicyclic structure-containing acid anhydrides such as 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (CHDA) and 1,2,4, 5-cyclobutanetetracarboxylic dianhydride (CBDA) as monomers and made into polyimide. Examples of fluorine-containing polyimides are: the polyimide resin is a compound containing, as a monomer, at least one or more of a fluorine-containing diamino compound such as 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl (TFMB) and the like, or a fluorine-containing acid anhydride such as 2, 2-bis (3, 4-anhydrous dicarboxyphenyl) hexafluoropropane (6FDA), 9-bis (trifluoromethyl) xanthene tetracarboxylic dianhydride (6FCDA), 9-phenyl-9- (trifluoromethyl) xanthene tetracarboxylic dianhydride (3FCDA) and the like, and is produced as a polyimide. More preferably, the polyimide contains fluorine, and still more preferably contains TFMB as a diamino compound containing fluorine and 6FDA as a fluorine-containing acid anhydride.
Any coating method may be used for forming the pre-polyimide resin layer. Further, a plurality of pre-polyimide resin layers may be formed on the hard support. When forming a plurality of layers, it is preferable that the precision of the film thickness and the like is high, and therefore the following 3 methods are preferable.
Method 1) 2 or more kinds of pre-polyimide resin layers are simultaneously formed using a multi-layer mold.
Method 2) after forming a pre-polyimide resin layer by any method, another pre-polyimide resin layer is formed on the non-dried coated surface by a doctor blade (knife coat) method, a die method, or the like.
Method 3) A pre-polyimide resin layer is formed by an arbitrary method, dried, and then another pre-polyimide resin layer is formed on the coated surface by an arbitrary method.
The blade coating method mentioned here is a method of spreading the resin solution by a bar (bar), a doctor blade (squeegee), a doctor blade (knife), or the like.
Any method may be used for curing the pre-polyimide resin layer. After the formation of the pre-polymerized imide resin layer, the hard support including the pre-dried pre-polymerized imide resin layer is left to stand at a high temperature for a certain time in a batch type heat drying furnace, or the moving speed of the laminate in the furnace of a continuous heat treatment apparatus is controlled to secure the time and temperature for drying and hardening, thereby forming a flexible substrate including a single-layered or multi-layered polyimide resin layer.
When the pre-polyimide resin layer is hardened, the pre-polyimide resin layer is heated to remove the solvent. Particularly, when a polyimide precursor resin solution is used, an imide bond is further formed by a ring-closure reaction (hereinafter referred to as "imidization"). The curing conditions are appropriately adjusted depending on the chemical structures of the polyimide and the polyimide precursor described later, the structure of the heat treatment apparatus, and the like, and when the heat treatment is rapidly performed at a high temperature, a skin layer is formed on the surface of the resin layer and the solvent is hard to evaporate or foam, so it is desirable to perform the heat treatment while gradually increasing from a low temperature to a high temperature.
When the pre-polyimide resin layer is a polyimide precursor, the heat treatment temperature is preferably low and the heat treatment time is preferably short, with respect to the heat treatment conditions during curing, in order to suppress thermal degradation of the flexible substrate and production cost in the production process. However, if the heat treatment temperature is too low or the heat treatment time is too short, the curing may not be sufficient, and therefore, it is preferable that the maximum temperature is 300 ℃ or more and the holding time at the maximum temperature is 2 minutes or more. In this temperature range, imidization proceeds with good efficiency. Further, adsorbates derived from atmospheric components, moisture, and the like distributed on the surface of the hard support can be sufficiently removed. More preferably, the maximum temperature is 320 ℃ or higher, and the holding time at the maximum temperature is 2 minutes or longer. Further, it is preferable that the maximum temperature is 360 ℃ or more and the holding time at the maximum temperature is 2 minutes or more.
On the other hand, when the pre-polyimide resin layer is a polyimide, the resin layer is cured by drying. Therefore, the heat treatment temperature may also be lower than in the case of the polyimide precursor. The heat treatment temperature in this case is preferably a maximum temperature of 280 ℃ or higher, more preferably 300 ℃ or higher.
The curing may be performed in an inert gas such as nitrogen or argon or in air. The reaction may be carried out under any of normal pressure, reduced pressure, increased pressure and vacuum.
In addition, the formation of the pre-polyimide resin layer and the formation of the flexible substrate may be continuously performed by a continuous heat treatment apparatus.
In the flexible substrate forming step, the hard support is subjected to a heat treatment, and then a resin solution is applied. The heat treatment of the hard support before the resin solution is applied is also referred to as "pre-heat treatment". By performing the pre-heat treatment, the flexible substrate is not peeled off from the hard support in the functional layer forming step, and the hard support can be removed from the flexible substrate without damaging the hard support, the flexible substrate, and the functional layer in the support removing step. Specifically, the peeling strength of the hard support and the flexible substrate is excessively high without the pre-heat treatment, and when the hard support is removed, damage such as damage or cracks may be caused to the hard support, the flexible substrate, or the functional layer.
The conditions of the pre-heat treatment vary depending on the hard support and the resin solution used, and the maximum temperature of the pre-heat treatment is preferably 300 ℃ or higher in view of removing impurities on the hard support and maintaining the peel strength of the hard support and the flexible substrate within an appropriate range. The maximum temperature of the preliminary heat treatment is more preferably 360 ℃ or higher. The environment during heating may be any of an atmosphere, an inert gas atmosphere, and a reduced pressure atmosphere, and is preferably an atmosphere from the viewpoint of suppressing the production cost and improving the removal efficiency of the surface of the hard support. In addition, for example, in the case of using glass as the hard support, the upper limit of the maximum temperature of the pre-heating treatment is substantially 500 ℃.
In order to prevent the adhesion of impurities or moisture to the hard support subjected to the heat treatment, it is preferable to apply a resin solution to the hard support within 180 minutes after the heat treatment is completed. More preferably within 120 minutes. On the other hand, if the resin solution is applied without a long time after the heat treatment, the flexible substrate may be expanded or deteriorated by the heat of the hard support. Therefore, it is preferable to apply the resin solution in a state where the temperature of the hard support is 40 ℃ or lower after the heat treatment. After the heat treatment described here, the time point is when the cooling of the hard support is started after the heat treatment. Examples of the cooling method include cooling by air blowing and forced cooling.
Next, the functional layer forming step will be described. And forming a functional layer on the flexible substrate obtained in the flexible substrate forming step. As the functional layer, a known device for securing the function of a flexible device can be used, and examples thereof include an organic EL Thin Film Transistor (TFT), a photoelectric conversion device, an electronic paper driving device, and a color filter. In the case of manufacturing an organic EL display as a flexible element, a functional layer may be a TFT for image driving. Examples of the material of the TFT include a silicon semiconductor and an oxide semiconductor. In the case of using no conventional flexible substrate, a barrier layer of an inorganic component is provided on a hard support such as a plate glass, and a TFT is formed thereon. When it is formed, high-temperature treatment (more than 300 ℃ and more than 400 ℃) is required. Therefore, it is also important for the flexible substrate to be resistant to such high temperature processing. In addition, for example, when a touch panel is manufactured as a flexible element, examples of the functional layer include an electrode layer such as a transparent conductive film or a metal mesh. Examples of the transparent conductive film include: tin-doped Indium Oxide (ITO), 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. Therefore, it is important for the flexible substrate to be resistant to such high temperature processing.
Next, the support removing step will be described. And removing the hard support from the flexible substrate on which the functional layer is formed. In the case of removing the functional layer, a notch line may be formed in a peripheral portion of the surface of a portion where the functional layer is formed on the flexible substrate (hereinafter referred to as "functional layer forming portion") by an arbitrary method to partition the frame body. By forming the slit line, the size and shape of the flexible substrate on which the functional layer is formed can be controlled. For example, when a plurality of functional layers are formed on one flexible substrate in order to improve manufacturing efficiency, the size and shape of the plurality of flexible substrates can be made uniform by forming a slit line. The smaller the area of the frame body is, the larger the area of the flexible substrate is, and the functional layer that can be formed on one flexible substrate can be increased. Therefore, the area of the frame is preferably small within a range in which the size and shape of the flexible substrate can be controlled.
Further, the flexible substrate in the inner region divided by the cut line is peeled from the rigid support together with the functional layer, and a flexible device having the functional layer on the flexible substrate is obtained. The peeling method may use a well-known method as long as the quality of the resulting flexible member is not degraded. The frame body can be peeled off by a known method. The flexible substrate and the frame may be peeled off first. In the case where the notch line is not formed, the entire flexible substrate is peeled off together with the functional layer.
As described above, the method for manufacturing a flexible element according to the present invention can appropriately control the peel strength of the rigid support and the flexible substrate by a simple method of heat treatment of the rigid support. As a result, the flexible element can be manufactured without damaging the rigid support, the flexible substrate, and the functional layer when the flexible element is separated from the rigid support. Therefore, the flexible element manufactured by the manufacturing method can be expected to have high manufacturing yield and long product life.
Next, a flexible element manufacturing apparatus of the present invention will be described. The flexible element manufacturing apparatus is characterized in that: the flexible substrate forming process is continuously performed. Specifically, the apparatus is provided with a device for continuously heat-treating the hard support at 300 ℃ or higher as shown in FIG. 1. The flexible element manufacturing apparatus 10 shown in fig. 1 will be described below as an example. When the rigid support 11 is placed on the conveyor belt (conveyor)16, the rigid support 11 moves in the direction of the arrow on the conveyor belt 16. In the 1 st continuous heat treatment apparatus 13, the hard support 11 is heated at a maximum temperature of 300 ℃ or higher (pre-heat treatment). After heating, the resin solution supplied from the resin solution supply device 14 is applied to the surface of the hard support 11. Then, the flexible substrate 12 is formed on the rigid support 11 by heating (post-heating treatment) in the 2 nd continuous heating treatment apparatus 15 at a maximum temperature of 300 ℃.
As another example, a flexible element manufacturing apparatus including the following steps 1 to 7 may be mentioned.
After heating, the hard support is taken out from the oven, and a resin solution is applied to the surface of the hard support by a coater.
(step 3) the hard support coated with the resin solution is dried by a vacuum dryer, a hot plate or an oven, and a pre-polymerized imide resin layer is formed on the hard support.
(step 4) the rigid support having the pre-polymerized imide resin layer formed thereon is introduced into a continuous heat treatment apparatus, and heated at a maximum temperature of 300 ℃ or higher to form a flexible substrate (post-heat treatment). The inside of the continuous heat treatment apparatus is conveyed by a conveyor belt or a roller made of metal.
(step 5) the rigid support on which the flexible substrate is formed is transferred to a functional layer forming apparatus, and the functional layer is formed in a continuous batch manner.
(step 6) the flexible substrate having the functional layer formed thereon is separated from the hard support by a peeling machine.
(step 7) the peeled hard support is washed and transferred to a stocker.
In the above steps 1 to 7, the hard support or the like may be moved by a robot or by a manual operation.
[ examples ]
The present invention will be specifically described below with reference to examples and comparative examples. In addition, the present invention is not limited by these matters.
1. Method for measuring various physical properties and testing performance
[ measurement of peeling Strength ]
Regarding the peel strength between the hard support and the polyimide resin layer, the laminate was cut into the polyimide side or subjected to patterning and etching on the substrate side with a line width (about 1mm to 30 mm) suitable for measurement, and the resin layer was peeled in the 180 ° direction using a tensile tester (stragraph-M1) manufactured by toyo seiki corp. Further, the case where the processed thin line was firmly adhered to the resin interface and was difficult to peel was evaluated as "non-peelable".
2. Synthesis of Polyamic acid (polyimide precursor) solution
Raw materials, aromatic diamino compounds, acid anhydride compounds of aromatic tetracarboxylic acids, acid anhydrides having alicyclic structures, and solvents used for the synthesis of polyamic acid (polyimide precursor) solutions used in the following synthesis examples or examples and comparative examples are shown below.
[ aromatic diamino Compound ]
4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl (TFMB)
4,4' -diaminodiphenyl ether (44DAPE)
[ acid anhydride Compound of aromatic tetracarboxylic acid ]
Pyromellitic anhydride (PMDA)
2, 2-bis (3, 4-Anhydrous dicarboxyphenyl) hexafluoropropane (6FDA)
2,3,2',3' -Biphenyltetracarboxylic dianhydride (BPDA)
[ acid anhydride having an alicyclic structure ]
1,2,4, 5-Cyclohexanetetracarboxylic dianhydride (CHDA)
[ solvent ]
N, N-Dimethylacetamide (DMAc)
Synthesis example 1
TFMB (15.8227g) was placed in a 300ml separable flask under a nitrogen stream, and was added to 170g of DMAc as a solvent with stirring, heated, and dissolved at 20 ℃. Then, 6FDA (7.5660g) and PMDA (6.6113g) were added. Thereafter, the solution was stirred at room temperature for 4 hours to effect polymerization, and 200g of a pale yellow viscous polyamic acid A varnish was obtained. Further, the polyamic acid a varnish was hardened under heating conditions described later, thereby obtaining a polyimide resin a.
Synthesis example 2
200g of a pale yellow viscous polyamic acid B varnish was obtained in the same manner as in Synthesis example 1 except that TFMB (16.93g) as an aromatic diamino compound, PMDA (10.12g) as an acid anhydride compound of an aromatic tetracarboxylic acid, and 6FDA (2.95g) were used. Further, the polyamic acid B varnish was hardened under heating conditions described later, thereby obtaining a polyimide resin B.
Synthesis example 3
200g of pale yellow viscous polyamic acid C varnish was obtained in the same manner as in Synthesis example 1, except that TFMB (12.54g) as an aromatic diamino compound and 6FDA (17.46g) as an acid anhydride compound of an aromatic tetracarboxylic acid were used. Further, the polyamic acid C varnish was hardened under heating conditions described later, thereby obtaining a polyimide resin C.
Synthesis example 4
200g of pale yellow viscous polyamic acid D varnish was obtained in the same manner as in Synthesis example 1, except that TFMB (12.31g) as an aromatic diamino compound and 6FDA (17.69g) as an acid anhydride compound of an aromatic tetracarboxylic acid were used. Further, the polyamic acid D varnish was hardened under heating conditions described later, thereby obtaining a polyimide resin D.
Synthesis example 5
200g of brown viscous polyamic acid E varnish was obtained in the same manner as in Synthesis example 1, except that 44DAPE (14.29g) as an aromatic diamino compound and BPDA (15.65g) as an acid anhydride compound of an aromatic tetracarboxylic acid were used. Further, the polyamic acid E varnish was hardened under heating conditions described later, thereby obtaining a polyimide resin E.
Synthesis example 6
200g of a pale yellow viscous polyamic acid F varnish was obtained in the same manner as in Synthesis example 1, except that TFMB (17.60g) as an aromatic diamino compound and CHDA (12.37g) as an alicyclic structure-containing acid anhydride were used. Further, the polyamic acid F varnish was hardened under heating conditions described later, thereby obtaining a polyimide resin F.
3. Formation of polyimide layer on support substrate and evaluation of Performance
The hard supports used in the following examples and comparative examples are shown below.
Alkali-free glass available from glass plate … Corning (Corning), trade name "Eagle XG", having a thickness of 500 μm
The polyamic acid varnish applied to the rigid support is dried on a hot plate at 70 to 100 ℃ and then heated to 360 ℃ for about 30 minutes from 100 ℃ to cure the varnish.
Example 1
After heating a clean glass sheet (15 cm. times.15 cm) in an oven at 360 ℃ for 60 minutes in the atmosphere, cooling in the atmosphere, wiping the surface with acetone, and then coating the surface with polyamic acid A varnish. The time from the end of heating to coating was 60 minutes. It was heated under the heating condition to form a flexible substrate having a thickness of 25 μm. Then, a notch line was formed on the flexible substrate using a dicing blade (cutter), and a frame of 10mm × 100mm was divided in the polyimide resin layer. Then, the flexible substrate in the inner region surrounded by the incision line is peeled. The peel strength is shown in table 1.
Examples 2 to 6
As shown in table 1 below, a flexible substrate having a thickness of 25 μm was formed and the flexible substrate was peeled off in the same manner as in example 1 except that polyamic acid B varnish was used in place of polyamic acid a varnish in example 2, polyamic acid C varnish was used in place of polyamic acid a varnish in example 1 (example 3), polyamic acid D varnish was used in place of polyamic acid a varnish in example 1 (example 4), polyamic acid E varnish was used in place of polyamic acid a varnish in example 1 (example 5), and polyamic acid F varnish was used in place of polyamic acid a varnish in example 1 (example 6) in example 1. The peel strength is shown in table 1.
Example 5
A flexible substrate having a thickness of 25 μm was formed in the same manner as in example 1, except that the substrate was heated in an oven at 300 ℃ for 60 minutes in the atmosphere, and the flexible substrate was peeled. The peel strength is shown in table 1.
Example 6
A flexible substrate having a thickness of 25 μm was formed in the same manner as in example 1 except that the polyamic acid a varnish was applied to the surface within 200 minutes after the heat treatment was completed, and the flexible substrate was peeled off. The peel strength is shown in table 1.
Comparative example 1
A flexible substrate was formed and peeled in the same manner as in example 1, except that the glass sheet was not heated. The results are shown in table 1.
[ Table 1]
As is clear from the results of the examples and comparative examples, a flexible substrate was formed by applying a resin solution after heat treatment of a hard support, and a good peel strength was obtained. Therefore, when the flexible substrate is formed on the hard support in this manner, the predetermined functional layer can be accurately provided in the subsequent functional layer forming step, and the flexible substrate can be easily removed from the hard support together with the functional layer in the support removing step, so that the flexible element can be manufactured easily at low cost.
Claims (5)
1. A method of manufacturing a flexible element, comprising the steps of: a flexible substrate forming step of forming a flexible substrate on a hard support by applying a resin solution on the hard support; a functional layer forming step of forming a functional layer on the flexible substrate; and a support removing step of removing the flexible substrate on which the functional layer is formed from the hard support together with the functional layer, wherein the method for manufacturing a flexible element is characterized in that:
in the flexible substrate forming step, the hard support is subjected to a heating treatment, and then a resin solution is applied, wherein the maximum temperature of the heating treatment is 300 ℃ to 500 ℃.
2. A method of manufacturing a flexible element according to claim 1, characterized in that: after the heat treatment is completed, the resin solution is applied to the hard support within 180 minutes.
3. A flexible member manufactured by the manufacturing method of a flexible member according to claim 1 or 2.
4. The flexible element of claim 3, wherein: the flexible element is a touch screen.
5. A flexible element manufacturing apparatus for the flexible element manufacturing method according to claim 1 or 2, characterized in that: the device comprises a device for continuously heating the hard support at 300 ℃ or higher, wherein the flexible element manufacturing device comprises a 1 st continuous heating device and a 2 nd continuous heating device, and the hard support before being coated with the resin solution is heated in the 1 st continuous heating device under the condition that the maximum temperature is 300 ℃ or higher and 500 ℃ or lower.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014073833 | 2014-03-31 | ||
| JP2014-073833 | 2014-03-31 |
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| Country | Link |
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| JP (1) | JP6548425B2 (en) |
| KR (1) | KR102365293B1 (en) |
| CN (1) | CN104952780B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106595269A (en) * | 2015-10-19 | 2017-04-26 | 上海绿特丹保温工程有限公司 | Belt type reciprocating dual-stroke drying machine |
| WO2018066508A1 (en) * | 2016-10-05 | 2018-04-12 | 日本電気硝子株式会社 | Method for producing glass resin laminate, and glass resin laminate |
| CN107565064B (en) * | 2017-07-28 | 2019-08-13 | 武汉华星光电半导体显示技术有限公司 | The production method of flexible display and the substrate for making flexible display |
| KR102571964B1 (en) * | 2017-12-15 | 2023-08-29 | 도레이 카부시키가이샤 | Manufacturing apparatus and manufacturing method of polymer thin film |
| CN111620296A (en) * | 2020-05-19 | 2020-09-04 | 中国科学院光电技术研究所 | High-flatness fixing method for adding uniform radial pre-tightening force to flexible film |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI660847B (en) | 2019-06-01 |
| KR102365293B1 (en) | 2022-02-21 |
| KR20150113926A (en) | 2015-10-08 |
| JP6548425B2 (en) | 2019-07-24 |
| TW201536556A (en) | 2015-10-01 |
| CN104952780A (en) | 2015-09-30 |
| JP2015199349A (en) | 2015-11-12 |
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