JP6334380B2 - Method for peeling resin film layer and method for manufacturing thin film element device - Google Patents

Description

  The present invention relates to a method for peeling a resin film layer and a method for manufacturing a thin film element device.

  In recent years, thin film element devices such as displays have been desired to be thin, lightweight, and flexible. In order to meet such a demand, it is necessary to form a thin film element on a resin substrate or a resin film. However, since a resin substrate and a resin film are inferior in heat resistance and chemical resistance as compared with a glass substrate, a method of directly forming a thin film element thereon cannot be employed. Therefore, in the manufacture of a thin film element device including a thin film element such as a thin film transistor (TFT), after forming a resin layer on the glass substrate, the thin film element is once formed on the resin layer and then peeled off from the glass substrate. Although a technique for transferring to the substrate has been developed, usually, the glass substrate and the resin layer have high adhesion, and therefore it is difficult to peel them off by physical force. Therefore, in Patent Document 1, an amorphous silicon layer is formed as a separation layer on a substrate, a thin film transistor is formed thereon, and then the separation layer is irradiated with laser light or the like to generate hydrogen to generate an interface between the separation layers. A technique for peeling a thin film transistor from a substrate by generating a void in the substrate is disclosed.

JP 2000-133809 A

However, in the technique of Patent Document 1, it is necessary to newly introduce a low-pressure CVD apparatus for forming a separation layer made of amorphous silicon and a laser apparatus for irradiating the separation layer with laser light. In addition, there is a problem that productivity is low. Furthermore, in the technique of Patent Document 1, there is a problem that if the substrate after the thin film transistor is peeled is reused, the cost for removing the separation layer is increased.
Accordingly, the present invention has been made to solve the above problems, and has a low initial cost, high productivity, and a resin film that can reuse a used substrate at a low cost. An object of the present invention is to provide a layer peeling method and a thin film element device manufacturing method.

  The method for peeling a resin film layer according to the present invention includes a step of forming a nanoparticle layer on a support substrate, a step of forming a resin film layer on the nanoparticle layer, and a step of peeling the resin film layer from the support substrate; Is provided.

  In addition, the method for manufacturing a thin film element device according to the present invention includes a step of forming a nanoparticle layer on a support substrate, a step of forming a resin film layer on the nanoparticle layer, and a thin film element on the resin film layer. A step of forming a thin film element layer including the step of peeling the resin film layer on which the thin film element layer is formed from the support substrate.

  According to the present invention, it is possible to provide a method for peeling a resin film layer and a method for manufacturing a thin film element device, which have low initial cost and high productivity, and can reuse a used substrate at low cost. it can.

It is a schematic diagram explaining each process of the peeling method of the resin film layer which concerns on Embodiment 1 of this invention. It is a figure explaining the example which controls the adhesive force of a support substrate and a resin film layer in the peeling method of the resin film layer which concerns on Embodiment 1 of this invention. It is a schematic diagram explaining each process of the manufacturing method of the thin film element device which concerns on Embodiment 2 of this invention. It is an observation result of the glass substrate after peeling in Example 1, and a resin film layer. It is an observation result of the glass substrate after peeling in the comparative example 1, and a resin film layer.

  Hereinafter, preferred embodiments of a method for peeling a resin film layer and a method for producing a thin film element device according to the present invention will be described with reference to the drawings.

Embodiment 1 FIG.
(A)-(c) of FIG. 1 is a schematic diagram explaining each process of the peeling method of the resin film layer which concerns on Embodiment 1 of this invention. In the method for peeling a resin film layer according to Embodiment 1, first, as shown in FIG. 1A, a nanoparticle layer is formed on a support substrate 10 (for example, quartz glass, heat resistant glass, etc.) having excellent heat resistance. 11 is formed. As a method for forming the nanoparticle layer 11, the nanoparticles 12 can be firmly attached to the surface of the support substrate 10 by intermolecular force or electrostatic force (when the resin film layer described later is formed, the nanoparticles 12 are supported by the support substrate 10). The method is not particularly limited as long as it is a technique that does not move above. However, the nanoparticle dispersion liquid is easy to form a uniform nanoparticle layer 11 and to easily control the amount of nanoparticles 12 attached. A method of drying after coating on the support substrate 10 is preferable. Examples of the method for applying the nanoparticle dispersion include spin coating, slit coating, roll coating, and ink jet. By increasing / decreasing the concentration of the nanoparticles 12 in the nanoparticle dispersion liquid or applying the nanoparticle dispersion liquid a plurality of times, the adhesion amount of the nanoparticles 12 on the support substrate 10 changes. The adhesion with the resin film layer can be controlled. Furthermore, the adhesive force between the support substrate 10 and a resin film layer to be described later can be controlled by providing a portion where the nanoparticle dispersion is applied and a portion where the nanoparticle dispersion is not applied on the support substrate 10. FIG. 2 shows an example of controlling the adhesion force between the support substrate 10 and the resin film layer. In FIG. 2, the adhesion strength of the peripheral edge 20 on the support substrate 10 is increased, and the adhesion strength of a portion other than the peripheral edge is reduced. In order to control the adhesion as described above, the nanoparticle dispersion is applied to a portion other than the peripheral portion on the support substrate 10 and dried, and then the nanoparticle concentration is lower than the nanoparticle dispersion previously applied. A method in which a low concentration nanoparticle dispersion is applied to the entire surface of the support substrate 10 and dried, and after the nanoparticle dispersion is applied to the entire surface of the support substrate 10 and dried, the periphery 20 on the support substrate 10 is dried. Examples include a method of removing the formed nanoparticle layer. The nanoparticle concentration of the nanoparticle dispersion may be set as appropriate according to the required adhesion, but is 2% by mass to 20% by mass from the viewpoint of coating properties and stability of the nanoparticle dispersion. It is preferable. As shown in FIG. 2, the peripheral edge 20 is increased in each step of the method for manufacturing a thin film element device by increasing the adhesion of the peripheral edge 20 on the support substrate 10 and reducing the adhesion of a portion other than the peripheral edge. The resin film layer 13 can be prevented from peeling off from the support substrate 10 and the resin film layer 13 can be easily peeled off from the support substrate 10 after completion of the process.

The nanoparticles 12 constituting the nanoparticle layer 11 may be appropriately selected from an inorganic material and an organic material according to temperature conditions when a thin film element is further formed on a resin film layer to be described later. from the point of _high, it is preferable that an inorganic material such as _{TiO 2, SiO 2, Al 2} O 3. The particle size of the nanoparticles 12 may be appropriately selected according to the use of the thin film element further formed on the resin film layer, but is usually about 1 nm to 100 nm when transparency is required for the resin film layer. The particle size must be smaller than the visible light wavelength, specifically 40 nm or less. Transparency can be maintained by using the nanoparticles 12 having a particle size of 40 nm or less.

  Next, as shown in FIG. 1B, a resin film layer 13 is formed on the nanoparticle layer 11. The formation method of the resin film layer 13 is not particularly limited as long as it is a technique capable of forming a heat-resistant resin film that can withstand a temperature of about 350 ° C. to 450 ° C., but an existing manufacturing apparatus is used as it is. Thus, a thin film element can be formed on the support substrate 10, and after the thin film element is completed, a flexible device can be manufactured without capital investment by peeling it from the support substrate 10. The method is preferred. Examples of the method for applying the resin varnish include a spin coating method, a slit coating method, a roll coating method, and an ink jet method. The resin constituting the resin varnish may be appropriately selected from a thermosetting resin and an ultraviolet curable resin, but polyimide and silsesquioxane are preferable from the viewpoint of high heat resistance and small dimensional variation due to heat. The thickness of the resin film layer is preferably 10 μm to 20 μm in total with the thickness of the support substrate 10 in that an existing manufacturing apparatus is used as it is.

  Finally, as shown in FIG. 1C, the resin film layer 13 is peeled from the support substrate 10. The peeling method is not particularly limited as long as it is a method of peeling by a physical force, but peeling is preferable because it does not damage a thin film element further formed on the resin film layer 13. Further, since the nanoparticle layer 11 does not remain on the support substrate 10 after the resin film layer 13 is peeled off (taken in the resin film layer 13 side), the support substrate 10 should be reused through a simple cleaning process. Is possible.

  The resin film layer peeling method according to Embodiment 1 does not require the introduction of a low-pressure CVD apparatus or a laser apparatus, and can be carried out using an existing apparatus such as a spin coater. In addition, since the support substrate after use can be reused by simple cleaning, the manufacturing cost can be reduced.

Embodiment 2. FIG.
FIGS. 3A to 3D are schematic views for explaining each step of the method for manufacturing the thin film element device according to the second embodiment of the present invention. 3A and 3B are the same as those in FIGS. 1A and 1B described in the first embodiment, and thus the description thereof is omitted here. In addition, as shown in FIG. 2, by increasing the adhesion force of the peripheral edge portion 20 on the support substrate 10 and reducing the adhesion force of portions other than the peripheral edge portion, the peripheral edge in each step of the thin film element device manufacturing method The peeling of the resin film layer 13 from the part 20 can be prevented, and the resin film layer 13 can be easily peeled off from the support substrate 10 after the process is completed.
As shown in FIG. 3C, a thin film element layer 14 including a thin film element is formed on the resin film layer 13. Here, the thin film element is an element formed by a thin film and performing a predetermined function, and includes, for example, a thin film transistor (TFT), an organic light emitting diode (OLED), and the like. Such a thin film element layer 14 can be formed according to a known method.
Next, as shown in FIG. 3D, the resin film layer 13 on which the thin film element layer 14 is formed is peeled from the support substrate 10. The peeling method is not particularly limited as long as it is a method of peeling by a physical force, but peeling is preferable because it does not damage the thin film element formed on the resin film layer 13. Thus, a thin film element device in which the thin film element layer 14 is formed on the resin film layer 13 can be obtained without damaging the thin film element layer. In addition, since the nanoparticle layer 11 does not remain on the support substrate 10 after peeling the resin film layer 13 on which the thin film element layer 14 is formed (taken in the resin film layer 13 side), the support substrate 10 is simple. It can be reused through a cleaning process.

  The thin film element device manufacturing method according to the second embodiment does not require the introduction of a low-pressure CVD apparatus or a laser apparatus, and can be carried out using an existing apparatus such as a spin coater. In addition, since the support substrate after use can be reused by simple cleaning, the manufacturing cost can be reduced.

Hereinafter, although an example and a comparative example explain the details of the present invention, the present invention is not limited to these examples.
<Example 1>
A glass substrate (41 mm × 41 mm × thickness 0.7 mm) as a supporting substrate was washed with a detergent or pure water, and then washed with UV. Subsequently, an aqueous dispersion of TiO ₂ particles having a particle size of 6 nm on a glass substrate using a spin coater with the number of revolutions set at 1000 rpm (TKS-203 manufactured by TEIKA CORPORATION, TiO ₂ concentration: 20% by mass) After coating, the nanoparticle layer was formed by drying at 100 ° C. for 3 minutes.
Next, a transparent polyimide varnish (KS-TD manufactured by Toyobo Co., Ltd.) was applied on the nanoparticle layer using a spin coater whose rotation speed was set to 1000 rpm, and then prebaked at 100 ° C. for 10 minutes, and then nitrogen. Under an atmosphere, post-baking was performed at 300 ° C. for 1 hour to form a resin film layer having a final thickness of about 10 μm.
When a tape was applied to the end of the formed resin film layer and pulled, the resin film layer could be completely peeled from the glass substrate. The observation result of the glass substrate and resin film layer after peeling is shown in FIG.

<Comparative Example 1>
A glass substrate (41 mm × 41 mm × thickness 0.7 mm) was washed with a detergent or pure water, and then washed with UV. Subsequently, after applying a transparent polyimide varnish (KS-TD manufactured by Toyobo Co., Ltd.) on a glass substrate using a spin coater whose rotation speed was set at 1000 rpm, it was pre-baked at 100 ° C. for 10 minutes, and then in a nitrogen atmosphere. And post-baking at 300 ° C. for 1 hour to form a resin film layer having a final thickness of about 10 μm.
When a tape was applied to the end portion of the formed resin film layer and pulled, the resin film layer was cracked (film cut) and could not be peeled off from the glass substrate. The observation result of the glass substrate and resin film layer after peeling is shown in FIG.

<Example 2>
An aqueous dispersion of TiO ₂ particles having a particle diameter of 6 nm (TKS-203, manufactured by Teika Co., Ltd., TiO ₂ concentration: 20% by mass) or diluted with water to obtain a TiO ₂ concentration of 2% by mass, 3% by mass, The nanoparticle layer was formed in the same manner as in Example 1 except that the aqueous dispersion changed to 4% by mass, 5% by mass, or 10% by mass was applied onto a glass substrate using a spin coater with a rotation speed set to 2000 rpm. Formed. Subsequently, a resin film layer was formed on the nanoparticle layer in the same manner as in Example 1.
A peel test (90 degree method) of the formed resin film layer was performed using MX-500N-E manufactured by Imada Co., Ltd., and the adhesion between the glass substrate and the resin film layer was measured. The results are shown in Table 1.

From these results, it can be seen that the adhesive force between the glass substrate and the resin film layer can be controlled by increasing or decreasing the TiO ₂ concentration.

<Example 3>
An aqueous dispersion of TiO ₂ particles having a particle diameter of 6 nm (TKS-203 manufactured by Teika Co., Ltd., TiO ₂ concentration: 20% by mass) was diluted with water to change the TiO ₂ concentration to 3% by mass and 5% by mass. An aqueous dispersion was prepared. Using a spin coater with a rotation speed set to 2000 rpm, an aqueous dispersion with a TiO ₂ concentration of 3% by mass was applied on a glass substrate, dried at 100 ° C. for 3 minutes, and then the rotation speed was adjusted to 2000 rpm. After applying an aqueous dispersion with a TiO ₂ concentration of 5% by mass using a spin coater set to 1, a nanoparticle layer was formed by drying at 100 ° C. for 3 minutes. Subsequently, a resin film layer was formed on the nanoparticle layer in the same manner as in Example 1.
A peel test (90 degree method) of the formed resin film layer was performed using MX-500N-E made by Imada Co., Ltd., and the adhesion between the glass substrate and the resin film layer was measured. Met. From this result, it was found that the adhesive force between the glass substrate and the resin film layer changes by applying the aqueous dispersion of TiO ₂ particles twice.

  DESCRIPTION OF SYMBOLS 10 Support substrate, 11 Nanoparticle layer, 12 Nanoparticle, 13 Resin film layer, 14 Thin film element layer, 20 Peripheral part.

Claims (8)

Forming a nanoparticle layer on a support substrate;
Forming a resin film layer on the nanoparticle layer;
From said supporting substrate a stripping method of said resin film layer tree fat film layer Ru and a step of peeling a
After the nanoparticle layer is partially coated with the nanoparticle dispersion on the support substrate and dried, a low concentration nanoparticle dispersion having a lower nanoparticle concentration than the nanoparticle dispersion is applied to the support substrate. A method for peeling a resin film layer, wherein the method is formed by applying to the entire surface and drying .   The method for peeling a resin film layer according to claim 1, wherein the nanoparticle layer is formed by applying a nanoparticle dispersion onto the support substrate and then drying the nanoparticle dispersion. The method for peeling a resin film layer according to claim 1 or 2 , wherein the nanoparticles constituting the nanoparticle layer are an inorganic material. The method for peeling a resin film layer according to any one of claims 1 to 3 , wherein a particle size of the nanoparticles constituting the nanoparticle layer is 40 nm or less. The said resin film layer is formed by making it harden | cure after apply | coating a resin varnish on the said nanoparticle layer, The peeling method of the resin film layer as described in any one of Claims 1-4 characterized by the above-mentioned. . The method for peeling a resin film layer according to claim 5 , wherein the resin varnish is a polyimide varnish. The method for peeling a resin film layer according to claim 1 , wherein the nanoparticle dispersion liquid to be partially applied is applied to a portion other than the peripheral portion on the support substrate. Forming a nanoparticle layer on a support substrate;
Forming a resin film layer on the nanoparticle layer;
Forming a thin film element layer including a thin film element on the resin film layer;
A method of manufacturing a thin-film element device that comprises a step of removing the resin film layer in which the thin film element layer has been formed from the support substrate,
After the nanoparticle layer is coated with the nanoparticle dispersion on a portion other than the peripheral edge on the support substrate and dried, the low-concentration nanoparticle dispersion having a lower nanoparticle concentration than the nanoparticle dispersion is used. A method for producing a thin film element device, wherein the thin film element device is formed by coating the entire surface of a support substrate and drying .

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