WO2015098888A1

WO2015098888A1 - Glass laminate body, and method for manufacturing electronic device

Info

Publication number: WO2015098888A1
Application number: PCT/JP2014/083997
Authority: WO
Inventors: 純一 ▲角▼田; 研一江畑
Original assignee: 旭硝子株式会社
Priority date: 2013-12-26
Filing date: 2014-12-22
Publication date: 2015-07-02
Also published as: TWI655092B; KR20160102172A; JPWO2015098888A1; TW201532823A; CN105848886B; CN105848886A

Abstract

　The present invention pertains to a glass laminated body that includes: a support substrate provided with a resin layer, the substrate having a support substrate and a polyimide resin layer (first polyimide resin layer) formed on the support substrate; and a glass substrate provided with a resin layer, said glass substrate having a glass substrate and a polyimide resin layer (second polyimide resin layer) formed on the glass substrate, the support substrate provided with a resin layer and the glass substrate provided with a resin layer being laminated so that the first polyimide resin layer in the support substrate provided with a resin layer, and the second polyimide resin layer in the glass substrate provided with a resin layer are brought into contact. The surface roughness (Ra) of each of the surface of the first polyimide resin layer on the side opposite the support substrate side and the surface of the second polyimide resin layer on the side opposite the glass substrate side is 2.0 nm or less.

Description

Glass laminate and method for manufacturing electronic device

The present invention relates to a glass laminate, and more particularly, to a glass laminate laminated such that polyimide resin layers are in contact with each other.
Moreover, this invention relates to the manufacturing method of an electronic device using this glass laminated body.

In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.

Therefore, conventionally, a method of forming a member for an electronic device (for example, a thin film transistor) on a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used.
However, in this method, for example, when the thickness of one glass substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is scraped off with an etching solution. Therefore, it is not preferable from the viewpoint of productivity and use efficiency of raw materials. In addition, in the method of thinning a glass substrate by the above chemical etching, if a fine scratch exists on the surface of the glass substrate, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.

Recently, in order to cope with the above problems, after preparing a glass laminate in which a thin glass substrate and a reinforcing plate are laminated and forming a member for an electronic device such as a display device on the thin glass substrate of the glass laminate, A method for separating a reinforcing plate from a thin glass substrate has been proposed. For example, in Patent Document 1, the reinforcing plate has a support plate and a silicone resin layer fixed on the support plate, and the silicone resin layer and the thin glass substrate are in close contact with each other in a peelable manner. The reinforcing plate separated from the thin glass substrate is peeled off from the interface between the silicone resin layer of the glass laminate and the thin glass substrate, and can be reused as a glass laminate by being laminated with a new thin glass substrate.

International Publication No. 2007/018028

With regard to the glass laminate including the glass substrate described in Patent Document 1, higher heat resistance has recently been required. As the electronic device members formed on the glass substrate of the glass laminate become more functional and complex, the temperature at which the electronic device members are formed becomes even higher, and the time exposed to the high temperatures also increases. It often takes a long time.
The glass laminate described in Patent Document 1 can withstand treatment at 350 ° C. for 1 hour in the air. However, according to the study by the present inventors, when the glass laminate produced with reference to Patent Document 1 is treated at 400 ° C. for 1 hour, the glass substrate is peeled from the surface of the silicone resin layer. In addition, the glass substrate is not peeled off from the surface of the silicone resin layer, and a part of the glass substrate is destroyed, or a part of the resin of the resin layer remains on the glass substrate, resulting in a decrease in productivity of the electronic device. There was a case.
Moreover, under the above heating conditions, foaming and whitening due to decomposition of the silicone resin layer occur. When such a resin layer is decomposed, impurities may be mixed into the electronic device when the electronic device is manufactured on the glass substrate. As a result, the yield of the electronic device may be reduced.

The present invention has been made in view of the above problems, and is excellent in adhesion of a glass substrate before high-temperature heat treatment, and can easily peel off a glass substrate after high-temperature heat treatment, and a resin layer It aims at providing the glass laminated body by which decomposition | disassembly of was suppressed.
Moreover, an object of this invention is to provide the manufacturing method of the electronic device using this glass laminated body.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, according to the first aspect of the present invention, there is provided a support substrate with a resin layer having a support substrate and a polyimide resin layer (first polyimide resin layer) formed on the support substrate, and a glass substrate and the glass. A glass substrate with a resin layer having a polyimide resin layer (second polyimide resin layer) formed on the substrate, the first polyimide resin layer in the support substrate with the resin layer, and the first in the glass substrate with the resin layer The support substrate with the resin layer and the glass substrate with the resin layer are laminated so that the two polyimide resin layers are in contact with each other, the surface of the first polyimide resin layer opposite to the support substrate side, and the first 2 A glass laminate in which the surface roughness Ra of the surface opposite to the glass substrate side of the polyimide resin layer is 2.0 nm or less.
In the first embodiment, the polyimide resin includes a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the formula (1) described below, The residue (X) of the carboxylic acid contains at least one group selected from the group consisting of the groups represented by the formulas (X1) to (X4) described later, and the residue (A) of the diamine is a formula described later It preferably contains at least one group selected from the group consisting of groups represented by (A1) to (A8).
In the first embodiment, the residue (X) of the tetracarboxylic acid includes at least one of a group represented by the following formula (X1) and a group represented by the following formula (X4), and is a residue of a diamine. It is preferable that (A) includes at least one of a group represented by the formula (A1) described later and a group represented by the formula (A6) described later.
1st aspect WHEREIN: It is preferable that a support base material is a glass plate.
The 2nd aspect of this invention forms the member for electronic devices on the surface of the glass substrate in the glass laminated body of the said 1st aspect, The member formation process which obtains the laminated body with a member for electronic devices,
A separation step of removing the supporting substrate with a resin layer from the laminate with the member for electronic devices and obtaining an electronic device having the second polyimide resin layer, the glass substrate, and the member for electronic devices, and a method for producing an electronic device It is.

According to the present invention, there is provided a glass laminate that has excellent adhesion to a glass substrate before high-temperature heat treatment, can easily peel off the glass substrate after high-temperature heat treatment, and suppresses decomposition of the resin layer. Can be provided.
Moreover, according to this invention, the manufacturing method of the electronic device using this glass laminated body can be provided.

FIG. 1 is a schematic cross-sectional view of an embodiment of a glass laminate according to the present invention. 2 (A) to 2 (E) are schematic cross-sectional views showing an embodiment of a method for manufacturing a glass laminate and an electronic device according to the present invention in the order of steps. FIG. 3 is a schematic diagram of a peel strength measuring apparatus.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.

As one of the features of the glass laminate of the present invention, a polyimide resin layer having a surface with a predetermined surface roughness (hereinafter, also simply referred to as “resin layer”) is disposed on a support base and a glass substrate, The point which has laminated | stacked resin layers is mentioned. When these resin layers are laminated, the adhesion between them is excellent. Further, such a resin layer is excellent in heat resistance during heat treatment, and it is difficult for the peel strength between the resin layers to increase even after the heat treatment, and the glass substrate can be easily peeled off.

FIG. 1 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
As shown in FIG. 1, the glass laminate 10 includes a support base 12 and a glass substrate 16, and a first polyimide resin layer 14 a (polyimide resin layer) and a second polyimide resin layer 14 b (polyimide) existing therebetween. A resin layer). The first polyimide resin layer 14a has one surface in contact with the support base 12 and the other surface in contact with the second polyimide resin layer 14b. In addition, the support base material 12 and the 1st polyimide resin layer 14a comprise the support base material 18 with a resin layer. The second polyimide resin layer 14b has one surface in contact with the glass substrate 16 and the other surface in contact with the first polyimide resin layer 14a. In addition, the glass substrate 16 and the 2nd polyimide resin layer 14b comprise the glass substrate 20 with a resin layer.
The two-layer portion composed of the support base 12 and the first polyimide resin layer 14a reinforces the glass substrate 20 with a resin layer in a member forming process for manufacturing a member for an electronic device such as a liquid crystal panel.

The glass laminate 10 is used until a member forming step described later. That is, the glass laminate 10 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 16b of the glass substrate 16. Thereafter, the glass laminate on which the electronic device member is formed is separated into the support substrate 18 with a resin layer and the electronic device 26, and the support substrate 18 with a resin layer does not become a part constituting the electronic device 26. A new glass substrate 20 with a resin layer is laminated on the support substrate 18 with a resin layer, and can be reused as a new glass laminate 10.

In addition, the 1st polyimide resin layer 14a is being fixed on the support base material 12, and the 1st polyimide resin layer 14a is laminated | stacked on the 2nd polyimide resin layer 14b so that peeling is possible (contact | adherence). In the present invention, there is a difference in peeling strength (that is, stress required for peeling) between the fixing and the peelable laminate (adhesion), and fixing means that the peeling strength is larger than the adhesion. That is, the peel strength at the interface between the first polyimide resin layer 14a and the support base 12 is greater than the peel strength at the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b. In other words, the peelable lamination (adhesion) means that the peelable layer can be peeled at the same time without causing peeling of the fixed surface.
More specifically, the interface between the support substrate 12 and the first polyimide resin layer 14a has a peel strength (x), and the interface between the support substrate 12 and the first polyimide resin layer 14a exceeds the peel strength (x). When stress in the peeling direction is applied, the interface between the support base 12 and the first polyimide resin layer 14a is peeled off. The interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b has a peeling strength (y), and the peeling between the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b exceeds the peeling strength (y). When a directional stress is applied, the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b peels off. As described above, the peel strength (x) is greater than the peel strength (y).

Moreover, the 2nd polyimide resin layer 14b is being fixed on the glass substrate 16, and the 2nd polyimide resin layer 14b is laminated | stacked on the 1st polyimide resin layer 14a so that peeling is possible (contact | adherence). That is, the peel strength at the interface between the second polyimide resin layer 14b and the glass substrate 16 is greater than the peel strength at the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b.
Therefore, when a stress is applied to the glass laminate 10 in the direction of peeling the support substrate 12 and the glass substrate 16, the glass laminate 10 is peeled off at the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b. And it isolate | separates into the support base material 18 with a resin layer, and the glass substrate 20 with a resin layer.

The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) increases the adhesion of the first polyimide resin layer 14a to the support substrate 12, and has a relatively higher adhesion than the second polyimide resin layer 14b after the heat treatment. It can be maintained.
In order to increase the adhesion of the first polyimide resin layer 14a to the support substrate 12, for example, as described later, a method of forming the first polyimide resin layer 14a on the support substrate 12 (preferably by thermosetting) This is performed by a method of forming a predetermined first polyimide resin layer 14a by curing a curable resin to be a polyimide resin containing a repeating unit represented by the formula (1) on the support substrate 12. The first polyimide resin layer 14a bonded to the support substrate 12 with a high bonding force can be formed by the adhesive force at the time of curing.
In addition, as a method of increasing the adhesion of the second polyimide resin layer 14b to the glass substrate 16, for example, as described later, a method of forming the second polyimide resin layer 14b on the glass substrate 16 (preferably by thermosetting). A method of curing a curable resin to be a polyimide resin containing a repeating unit represented by the formula (1) on the glass substrate 16 to form a predetermined second polyimide resin layer 14b).
On the other hand, the bonding force of the cured first polyimide resin layer 14a to the second polyimide resin layer 14b is generally lower than the bonding force generated during the curing. Therefore, by manufacturing the support substrate 18 with a resin layer and the glass substrate 20 with a resin layer, and then laminating both so that the first polyimide resin layer 14a and the second polyimide resin layer 14b are in contact with each other, A glass laminate 10 that satisfies a desired peel strength relationship can be manufactured.

Below, each layer (the support base material 12, the glass substrate 16, the 1st polyimide resin layer 14a, and the 2nd polyimide resin layer 14b) which comprises the glass laminated body 10 is explained in full detail first, Then, a glass laminated body and electronic A device manufacturing method will be described in detail.

[Supporting substrate]
The support substrate 12 supports and reinforces the glass substrate 16, and deformation and scratches of the glass substrate 16 are formed during the formation of the electronic device member in a member forming step (step of obtaining a laminated body with an electronic device member) described later. Prevent sticking and damage.
As the support substrate 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. Usually, since the member forming process involves heat treatment, the support base 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 16 and more preferably formed of the same material as the glass substrate 16. preferable. That is, the support base 12 is preferably a glass plate. In particular, the support base 12 is preferably a glass plate made of the same glass material as the glass substrate 16.

The thickness of the support base 12 may be thicker or thinner than the glass substrate 16. Preferably, the thickness of the support base 12 is based on the thickness of the glass substrate 16, the thickness of the first polyimide resin layer 14a, the thickness of the second polyimide resin layer 14b, and the thickness of the glass laminate 10. Selected. For example, the current member forming process is designed to process a substrate having a thickness of 0.5 mm. The thickness of the glass substrate 16, the thickness of the first polyimide resin layer 14a, and the thickness of the second polyimide resin layer 14b When the sum with the thickness is 0.1 mm, the thickness of the support base 12 is set to 0.4 mm. In general, the thickness of the support base 12 is preferably 0.2 to 0.5 mm, and is preferably thicker than the glass substrate 16.

When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons such as being easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.

The difference in average linear expansion coefficient between the support base 12 and the glass substrate 16 at 25 to 300 ° C. is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably 300 × 10 ⁻⁷ / ° C. or less. More preferably, it is 200 × 10 ⁻⁷ / ° C. or less. If the difference is too large, the glass laminate 10 may be severely warped or the support substrate 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming process. When the material of the support base material 12 is the same as the material of the glass substrate 16, it can suppress that such a problem arises.

[Glass substrate]
In the glass substrate 16, the second polyimide resin layer 14b is disposed on the first main surface 16a, and the electronic device member is provided on the second main surface 16b opposite to the second polyimide resin layer 14b. That is, the glass substrate 16 is a substrate used for forming an electronic device described later.
The glass substrate 16 may be of a general type, and examples thereof include a glass substrate for a display device such as an LCD or an OLED. The glass substrate 16 is excellent in chemical resistance and moisture permeability and has a low heat shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.
The contents of JIS R 3102 (revised in 1995) are incorporated herein by reference.

If the linear expansion coefficient of the glass substrate 16 is large, the member forming process often involves heat treatment, and various inconveniences are likely to occur. For example, when a thin film transistor (TFT) is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed is cooled under heating, the TFT may be excessively misaligned due to thermal contraction of the glass substrate 16. .

The glass substrate 16 is obtained by melting a glass raw material and molding the molten glass into a plate shape. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used. The glass substrate 16 having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature and then stretching it by means of stretching or the like to make it thin (redraw method).

The type of glass of the glass substrate 16 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.

As the glass of the glass substrate 16, glass suitable for the type of electronic device member and the manufacturing process thereof is employed. For example, a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). Thus, the glass of the glass substrate 16 is appropriately selected based on the type of device to be applied and its manufacturing process.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.10 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. It is. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up.
Further, the thickness of the glass substrate 16 is preferably 0.01 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.

The glass substrate 16 may be composed of two or more layers. In this case, the material forming each layer may be the same material or a different material. In this case, “the thickness of the glass substrate 16” means the total thickness of all the layers.

[Resin layer (first polyimide resin layer and second polyimide resin layer)]
The first polyimide resin layer 14a and the second polyimide resin layer 14b prevent misalignment of the glass substrate 16 until the operation of separating the glass substrate 16 and the supporting base material 12 is performed, and the glass substrate 16 and the like are separated. To prevent damage. The first polyimide resin layer 14a and the second polyimide resin layer 14b are laminated (adhered) so as to be peelable. As described above, the first polyimide resin layer 14a and the second polyimide resin layer 14b are bonded with a weak bonding force, and the peel strength at the interface is between the first polyimide resin layer 14a and the support substrate 12. Lower than the peel strength at the interface and the peel strength at the interface between the second polyimide resin layer 14 b and the glass substrate 16.
That is, when separating the glass substrate 16 and the support base material 12, the glass substrate 16 is peeled off at the interface between the first polyimide resin layer 14 a and the second polyimide resin layer 14 b, and the support base material 12 and the first polyimide resin layer 14 a are separated. And at the interface between the glass substrate 16 and the second polyimide resin layer 14b. For this reason, although the 1st polyimide resin layer 14a and the 2nd polyimide resin layer 14b contact | adhere, it has the surface characteristic which can be peeled easily. That is, the first polyimide resin layer 14a and the second polyimide resin layer 14b are bonded to each other with a certain bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off. The glass substrate 16 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16. In the present invention, this property of easily peeling off the surface is referred to as peelability. On the other hand, the support base 12 and the first polyimide resin layer 14a, and the glass substrate 16 and the second polyimide resin layer 14b are bonded with a bonding force that is relatively difficult to peel.

It is thought that the 1st polyimide resin layer 14a and the 2nd polyimide resin layer 14b are couple | bonded by the bond strength resulting from weak adhesive force or van der Waals force.
In some cases, the surface of the first polyimide resin layer 14a or the surface of the second polyimide resin layer 14b before lamination can be laminated by performing a treatment for weakening the bonding force between them.

The first polyimide resin layer 14a is bonded to the surface of the support base 12 with a strong bonding force such as an adhesive force or an adhesive force. Improvement of the adhesive force between the first polyimide resin layer 14a and the support substrate 12 is achieved by forming the first polyimide resin layer 14a on the support substrate 12. For example, as will be described later, a thermosetting polyimide resin is cured on the surface of the support base 12 by curing a curable resin that becomes a polyimide resin containing a repeating unit represented by the formula (1) by thermosetting, thereby supporting the support base material. It is possible to obtain a high bonding force by adhering to 12 surfaces. Moreover, a high bond strength can also be obtained by bringing a composition containing a polyimide resin into contact with the surface of the support substrate 12 and performing heat treatment as necessary to form the first polyimide resin layer 14a. Moreover, the process (for example, process using a coupling agent) which produces strong bond strength between the support base material 12 surface and the 1st polyimide resin layer 14a is given, and the support base material 12 surface and the 1st polyimide resin layer It is also possible to increase the binding force between the 14a.
The second polyimide resin layer 14b is also bonded to the surface of the glass substrate 16 with a strong bonding force such as an adhesive force or an adhesive force, like the first polyimide resin layer 14a.

At least one of the thickness of the first polyimide resin layer 14a and the thickness of the second polyimide resin layer 14b penetrates the blade between the first polyimide resin layer 14a and the second polyimide resin layer 14b at the time of peeling. Therefore, the thickness is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more from the viewpoint of peelability. The upper limit is not particularly limited, but is usually preferably 100 μm or less.
When the thickness of one of the first polyimide resin layer 14a and the second polyimide resin layer 14b is in the above range, the other thickness is not particularly limited, and is preferably 0.1 to 100 μm, for example, More preferably, it is 5 to 50 μm, and further preferably 1 to 20 μm. When the thicknesses of the first polyimide resin layer 14a and the second polyimide resin layer 14b are within such a range, bubbles and foreign matters may be interposed between the first polyimide resin layer 14a and the second polyimide resin layer 14b. Even if it exists, generation | occurrence | production of the distortion defect of the glass substrate 16 can be suppressed.
In addition, the said thickness intends average thickness, measures the thickness of the arbitrary 5 points | pieces of the 1st polyimide resin layer 14a (or 2nd polyimide resin layer 14b), and arithmetically averages them.

The surface roughness Ra of the surface 114a of the first polyimide resin layer 14a opposite to the support substrate 12 side and the surface 114b of the second polyimide resin layer 14b opposite to the glass substrate 16 side is 2.0 nm. It is below, and 1.5 nm or less is preferable and 1.0 nm or less is more preferable at the point which the adhesiveness of the support base material 18 with a resin layer and the glass substrate 20 with a resin layer is more excellent. The lower limit is not particularly limited, but is preferably 0 nm.
When the surface roughness Ra is more than 2.0 nm, the adhesion between the first polyimide resin layer 14a and the second polyimide resin layer 14b is poor.
In general, the method of forming a polyimide resin into a layered form is a method of extrusion molding after producing a thermoplastic polyimide resin, or after applying a solution containing a curable resin that becomes a polyimide resin by thermosetting on a substrate. There is a method of curing on the substrate surface. In the present invention, a resin layer having a surface roughness Ra in the above range is easily obtained by molding the resin layer by the latter method.
Here, the surface roughness Ra is measured by an atomic force microscope (manufactured by Pacific Nanotechnology, Nano Scope IIIa; Scan Rate 1.0 Hz, Sample Lines 256, Off-line Modify Flatten order-2, Planefit order-2). (Measurement method of surface roughness of fine ceramic thin film by atomic force microscope JIS R 1683: 2007 compliant)
Note that the contents of JIS R 1683: 2007 are incorporated herein by reference.

Reasons for Ra to be increased are (1) intrinsic type (additives), (2) film surface roughness due to foaming, and (3) environmental factors (foreign substances). As a countermeasure of (1), it is preferable to use a glass substrate having a smooth surface as a precondition and not to use a lubricant or filler in the coating solution. The application method is not particularly limited, but it is preferable to apply using, for example, a die coater. If the solvent is dried too quickly, foaming occurs, causing the problem (2). As a countermeasure, a film having a smooth surface can be obtained by optimizing the drying temperature and time. In Examples described later, after preliminary drying on a hot plate at 80 ° C. for 30 minutes and 120 ° C. for 30 minutes, heating was performed at 350 ° C. for 1 hour in a hot air drying furnace. The heating conditions are not limited to the above process. Further, since foreign matter may cause surface roughness, manufacturing in a clean room is suitable as a countermeasure for (3).

The structure of the polyimide resin in the first polyimide resin layer 14a and the second polyimide resin layer 14b is not particularly limited, but the residue of tetracarboxylic acids (X) and the residue of diamines represented by the following formula (1) It is preferable that the repeating unit which has (A) is included. In addition, although it is preferable that a polyimide resin contains the repeating unit represented by Formula (1) as a main component (95 mol% or more is preferable with respect to all the repeating units), other repeating units other than that (for example, And a repeating unit represented by the formula (2-1) or (2-2) described later.
The tetracarboxylic acid residue (X) is a tetracarboxylic acid residue obtained by removing a carboxy group from a tetracarboxylic acid, and the diamine residue (A) is a diamine obtained by removing an amino group from a diamine. Intended for residues.

In formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxy group from tetracarboxylic acids, and A represents a diamine residue obtained by removing an amino group from diamines.

In the formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxy group from tetracarboxylic acids, and at least one selected from the group consisting of groups represented by the following formulas (X1) to (X4) Preferably it contains a group. Among them, the peelability between the first polyimide resin layer 14a and the second polyimide resin layer 14b, or the heat resistance of the first polyimide resin layer 14a and the second polyimide resin layer 14b is more excellent (hereinafter simply referred to as “the present invention”). From the group consisting of groups represented by the following formulas (X1) to (X4): 50 mol% or more (preferably 80 to 100 mol%) of the total number of X More preferably, it comprises at least one selected group. More preferably, substantially all (100 mol%) of the total number of X is composed of at least one group selected from the group consisting of groups represented by the following formulas (X1) to (X4).
A represents a diamine residue obtained by removing an amino group from diamines, and preferably contains at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8). Among them, the group consisting of groups represented by the following formulas (A1) to (A8) in which 50 mol% or more (preferably 80 to 100 mol%) of the total number of A is more excellent in the effect of the present invention. More preferably, it comprises at least one group selected from: It is more preferable that substantially all (100 mol%) of the total number of A is composed of at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8).

From the standpoint of more excellent effects of the present invention, 80 to 100 mol% of the total number of X comprises at least one group selected from the group consisting of groups represented by the following formulas (X1) to (X4). In addition, it is preferable that 80 to 100 mol% of the total number of A is composed of at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8). In particular, the total number (100 mol%) is composed of at least one group selected from the group consisting of groups represented by the following formulas (X1) to (X4), and substantially the total number of A (100 More preferably, the mol%) comprises at least one group selected from the group consisting of groups represented by the following formulas (A1) to (A8).

Among these, X is preferably a group represented by the formula (X1) and a group represented by the formula (X4), and more preferably a group represented by the formula (X1) in that the effect of the present invention is more excellent. preferable.
Further, as A, the group represented by the formula (A1) and the group represented by the formula (A6) are preferable, and the group represented by the formula (A1) is more preferable in that the effect of the present invention is more excellent. .

As a polyimide resin comprising a suitable combination of the groups represented by the formulas (X1) to (X4) and the groups represented by the formulas (A1) to (A8), X represents a group represented by the formula (X1) A polyimide resin 1 in which A is a group represented by the formula (A1), and a polyimide in which X is a group represented by the formula (X4) and A is a group represented by the formula (A6) Resin 2 is preferred. In the case of the polyimide resin 1, it is more excellent in heat resistance. Moreover, in the case of the polyimide resin 2, it is preferable at the point of colorless transparency.

The number of repeating units (n) represented by the above formula (1) in the polyimide resin is not particularly limited, but is preferably an integer of 2 or more, and the first polyimide resin layer 14a and the second polyimide resin layer 14b. In view of the heat resistance of the coating film and the film formability of the coating film, it is preferably 10 to 10,000, more preferably 15 to 1,000.

The polyimide resin may contain at least one selected from the group consisting of the groups exemplified below as the residue (X) of the tetracarboxylic acids within a range that does not impair the heat resistance. Moreover, 2 or more types of groups illustrated below may be included.

In addition, the polyimide resin may contain one or more selected from the group consisting of the groups exemplified below as the residue (A) of the diamine, as long as the heat resistance is not impaired. Moreover, 2 or more types of groups illustrated below may be included.

The content of the polyimide resin in the first polyimide resin layer 14a and the second polyimide resin layer 14b is not particularly limited, but is 50 to 100% by mass with respect to the total mass of the resin layer in that the effect of the present invention is more excellent. Preferably, it is 75 to 100% by mass, more preferably 90 to 100% by mass.

In the 1st polyimide resin layer 14a and the 2nd polyimide resin layer 14b, other components (for example, the filler etc. which do not inhibit heat resistance) other than the said polyimide resin may be contained as needed.
Examples of fillers that do not impair heat resistance include fibrous fillers and non-fibrous fillers such as plate-like, scale-like, granular, indeterminate, and crushed products. Specifically, for example, glass fiber , PAN and pitch carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, locks Wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flake, glass microballoon, clay, molybdenum disulfide, wollastonite, Titanium oxide, zinc oxide, polyri Calcium acid, graphite, metal powders, metal flakes, metal ribbons, metal oxides, carbon powder, graphite, carbon flake, scaly carbon, and and carbon nanotubes. Specific examples of the metal powder, metal flake, metal ribbon, and metal oxide metal species include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

In addition, it is preferable that the 1st polyimide resin layer 14a and the 2nd polyimide resin layer 14b are layers of the polyimide resin formed by heat-processing to the layer of curable resin used as the polyimide resin by thermosetting, Furthermore, in the layer of the curable resin used as the polyimide resin containing the repeating unit which has the residue (X) of tetracarboxylic acids represented by the said Formula (1), and the residue (A) of diamines by thermosetting. More preferably, it is a polyimide resin layer formed by heat treatment. In addition, you may implement heat processing in steps, changing temperature.
The method for producing the first polyimide resin layer 14a and the second polyimide resin layer 14b will be described in detail in the method for producing a glass laminate at the subsequent stage.

[Method for producing glass laminate]
As a manufacturing method of the glass laminated body 10 of this invention, for example, the 1st polyimide resin layer 14a is formed on the support base material 12 using the curable resin mentioned later, and glass is used using the curable resin mentioned later. The second polyimide resin layer 14b is formed on the substrate 16, and then the support substrate 18 with the resin layer and the glass substrate with the resin layer so that the first polyimide resin layer 14a and the second polyimide resin layer 14b are in contact with each other. 20 is laminated | stacked and the glass laminated body 10 is manufactured.
When the curable resin is cured on the surface of the support substrate 12, the first polyimide resin layer 14a and the support substrate 12 are bonded to each other by the interaction with the surface of the support substrate 12 during the curing reaction, and the first polyimide resin layer 14a. It is thought that the peel strength between the support substrate 12 and the surface of the support substrate 12 increases. The same applies to the case where the curable resin is cured on the surface of the glass substrate 16.
Hereinafter, a step of forming the first polyimide resin layer 14a on the support base 12 using a curable resin described later is a first resin layer forming step, and a step of forming a second polyimide resin layer 14a on the glass substrate 16 using a curable resin layer described later. The step of forming the polyimide resin layer 14b is referred to as a second resin layer forming step, and the step of obtaining the glass laminate 10 by laminating the support substrate 18 with a resin layer and the glass substrate 20 with a resin layer is referred to as a lamination step. Will be described in detail.
In addition, below, although the aspect using curable resin is explained in full detail, it is not limited to this, A predetermined polyimide resin is made to contact on the support base material 12 (or glass substrate 16), and it heats as needed. You may form the 1st polyimide resin layer 14a (or 2nd polyimide resin layer 14b) by giving a process. In particular, when a solution in which a polyimide resin is dissolved in a solvent is used, it is preferable to perform heat treatment in order to volatilize the solvent. You may implement the lamination process mentioned later using the support base material with a resin layer and glass substrate with a resin layer which were obtained by this process.

(First resin layer forming step)
A 1st resin layer formation process is a process of obtaining the layer of a polyimide resin by performing heat processing to the layer of curable resin which becomes a polyimide resin by thermosetting formed on the support base material. As described above, the polyimide resin preferably includes a repeating unit represented by the formula (1) and having a tetracarboxylic acid residue (X) and a diamine residue (A). It is preferable that the residue (X) of the carboxylic acid includes at least one group selected from the group consisting of the groups represented by the above formulas (X1) to (X4), and the residue (A) of the diamine is the above It preferably contains at least one group selected from the group consisting of groups represented by formulas (A1) to (A8). As shown in FIG. 2A, in this step, the first polyimide resin layer 14a is formed on the surface of at least one side of the support base 12.
Hereinafter, the resin layer forming step will be described by dividing it into the following two steps.
Step (1): Step (2) of applying a curable resin, which becomes a polyimide resin containing the repeating unit represented by the above formula (1), to the support substrate 12 by thermosetting to obtain a coating film: The process which heat-processes a coating film and forms the 1st polyimide resin layer 14a Hereinafter, the procedure of each process is explained in full detail.

(Process (1): Coating film forming process)
Step (1) is a step of obtaining a coating film by applying a curable resin, which becomes a polyimide resin having a repeating unit represented by the above formula (1), by thermosetting on the support substrate 12.
The curable resin preferably contains a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine, and at least a part of the tetracarboxylic dianhydride is represented by the following formulas (Y1) to (Y4). ) Is preferably at least one tetracarboxylic dianhydride selected from the group consisting of compounds represented by the following formulas, wherein at least part of the diamines is represented by the following formulas (B1) to (B8): It is preferably at least one diamine selected from the group consisting of

The polyamic acid is usually represented as a structural formula containing a repeating unit represented by the following formula (2-1) and / or formula (2-2). In the formulas (2-1) and (2-2), the definitions of X and A are as described above.

The reaction conditions of tetracarboxylic dianhydride and diamines are not particularly limited, and are preferably reacted at −30 to 70 ° C. and reacted at −20 to 40 ° C. from the viewpoint that polyamic acid can be efficiently synthesized. Is more preferable.
The mixing ratio of the tetracarboxylic dianhydride and the diamine is not particularly limited, but the tetracarboxylic dianhydride is preferably 0.66 to 1.5 mol, more preferably 0. 9 to 1.1 mol, more preferably 0.97 to 1.03 mol is reacted.
In the reaction of tetracarboxylic dianhydride and diamines, an organic solvent may be used as necessary. The type of organic solvent to be used is not particularly limited. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, Dioxane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone and the like can be used, and two or more kinds may be used in combination.

In the reaction, if necessary, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride selected from the group consisting of the compounds represented by the above formulas (Y1) to (Y4) are added. You may use together.
In the above reaction, if necessary, other diamines other than diamines selected from the group consisting of the compounds represented by the above formulas (B1) to (B8) may be used together. Good.

In addition to the polyamic acid obtained by reacting the tetracarboxylic dianhydride and diamine, the curable resin used in this step is a tetracarboxylic dianhydride or diamine that can react with the polyamic acid. May also be included. When tetracarboxylic dianhydride or diamine is added in addition to polyamic acid, two or more polyamic acid molecules having a repeating unit represented by formula (2-1) or formula (2-2) are converted to tetracarboxylic acid diacid. It can be coupled via anhydrides or diamines.
In the case of having an amino group at the terminal of the polyamic acid, tetracarboxylic dianhydride may be added, and added so that the carboxyl group is 0.9 to 1.1 mol with respect to 1 mol of the polyamic acid. It's okay. In the case of having a carboxyl group at the terminal of the polyamic acid, a diamine may be added, and the amino group may be added in an amount of 0.9 to 1.1 mol with respect to 1 mol of the polyamic acid. In addition, when it has a carboxyl group at the terminal of polyamic acid, the acid terminal may be obtained by adding water or any alcohol to open the terminal acid anhydride group.
The tetracarboxylic dianhydride to be added later is more preferably a compound represented by the formulas (Y1) to (Y4). The diamines to be added later are preferably diamines having an aromatic ring, and more preferably compounds represented by the formulas (B1) to (B8).
When tetracarboxylic dianhydrides or diamines are added later, the polymerization degree (n) of the polyamic acid having a repeating unit represented by the formula (2-1) or the formula (2-2) is 1 to 20 Is preferred. When the polymerization degree (n) is within this range, the viscosity of the curable resin solution can be reduced even if the polyamic acid concentration in the curable resin solution is 30% by mass or more.

In this step, components other than the curable resin may be used.
For example, a solvent may be used. More specifically, the curable resin may be dissolved in a solvent and used as a curable resin solution (curable resin solution). As the solvent, an organic solvent is particularly preferable from the viewpoint of the solubility of the polyamic acid. As an organic solvent used, the organic solvent used in the case of the reaction mentioned above is mentioned.
In addition, when the organic solvent is contained in the curable resin solution, the content of the organic solvent is not particularly limited as long as the thickness of the coating film can be adjusted and the coating property can be improved. 5 to 95% by mass is preferable with respect to the total mass of the solution, and 10 to 90% by mass is more preferable.
Further, if necessary, a dehydrating agent or a dehydrating ring closure catalyst for promoting dehydration ring closure of the polyamic acid may be used together. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example.
Moreover, you may include the filler which does not inhibit the above-mentioned heat resistance.

The method for applying the curable resin (or curable resin solution) on the surface of the support substrate 12 is not particularly limited, and a known method can be used. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating.
The thickness of the coating film obtained by the above treatment is not particularly limited, and is appropriately adjusted so that the first polyimide resin layer 14a having the desired thickness described above can be obtained.

(Process (2): Heat treatment process)
Step (2) is a step of forming the first polyimide resin layer 14a by subjecting the coating film to heat treatment. By carrying out this step, for example, a ring closing reaction of polyamic acid contained in the curable resin proceeds, and a desired resin layer is formed.
The method for the heat treatment is not particularly limited, and a known method (for example, a method in which a support substrate with a coating film is left standing in a heating oven and heated) is appropriately used.
The heating temperature is not particularly limited, but is preferably 250 ° C. or higher and 500 ° C. or lower. The residual solvent ratio is lowered, the imidization ratio is further increased, and the effect of the present invention is further improved. Is more preferable.
The heating time is not particularly limited, and an optimal time is appropriately selected depending on the structure of the curable resin to be used. However, the residual solvent ratio is lowered, the imidization ratio is further increased, and the effect of the present invention is further improved. In this respect, 15 to 120 minutes are preferable, and 30 to 60 minutes are more preferable.
The heating atmosphere is not particularly limited, and is performed, for example, in the air, under vacuum, or under an inert gas.
Note that the heat treatment may be performed stepwise at different temperatures.
In addition, you may implement the drying heat processing for removing the volatile component (solvent) in a coating film before the process at the said heating temperature as needed. The temperature condition of the drying heat treatment is not particularly limited, but the heat treatment at 40 ° C. to 200 ° C. is preferable in that the effect of the present invention is more excellent. Further, the drying time is not particularly limited, and is preferably 15 to 120 minutes, more preferably 30 to 60 minutes, from the viewpoint that the effect of the present invention is more excellent. Note that the drying heat treatment may be performed stepwise at different temperatures.
Therefore, as one preferred embodiment of this step (2), there is an embodiment in which after the drying heat treatment at the above temperature is carried out, the above heat treatment at 250 ° C. or more and 500 ° C. or less is further carried out.

By passing through the said process (2), the 1st polyimide resin layer 14a containing a polyimide resin is formed.
Although the imidation ratio of a polyimide resin is not particularly limited, it is preferably 99.0% or more and more preferably 99.5% or more in terms of more excellent effects of the present invention.
The method for measuring the imidization rate is as follows. When the curable resin is heated at 350 ° C. for 2 hours in a nitrogen atmosphere, the imidization rate is 100%, and the peak intensity that remains unchanged before and after the heat treatment in the IR spectrum of the curable resin (for example, a peak derived from a benzene ring: for about 1500 cm ^-1), a peak derived from the imide carbonyl group: obtaining the imidization ratio by the intensity ratio of a peak intensity of about 1780 cm ^-1.

(Second resin layer forming step)
The second resin layer forming step is a step of obtaining a second polyimide resin layer by performing heat treatment on the curable resin layer that is formed on the glass substrate and becomes a polyimide resin by thermosetting. In addition, as above-mentioned, it is preferable that a polyimide resin contains the repeating unit which has the residue (X) of tetracarboxylic acids and the residue (A) of diamine represented by Formula (1). In this step, by performing the same procedure as the first resin layer forming step described above (the coating film forming step and the heat treatment step), as shown in FIG. 2B, at least on one side of the glass substrate 16 The second polyimide resin layer 14b is formed.

(Lamination process)
In the laminating step, the supporting substrate 18 with a resin layer obtained in the first resin layer forming step and the glass substrate 20 with a resin layer obtained in the second resin layer forming step are laminated to form a supporting substrate 12. In this step, the glass laminate 10 including the first polyimide resin layer 14a, the second polyimide resin layer 14b, and the glass substrate 16 in this order is obtained. More specifically, as shown in FIG. 2C, the surface 114a of the first polyimide resin layer 14a opposite to the support base 12 side and the glass substrate 16 side of the second polyimide resin layer 14b are The first polyimide resin layer 14a and the second polyimide resin layer 14b are laminated using the opposite surface 114b as a lamination surface to obtain the glass laminate 10.

The method in particular of laminating | stacking the support base material 18 with a resin layer and the glass substrate 20 with a resin layer is not restrict | limited, A well-known method is employable.
For example, the method of superimposing the 2nd polyimide resin layer 14b in the glass substrate 20 with a resin layer on the surface of the 1st polyimide resin layer 14a in the support base material 18 with a resin layer under a normal pressure environment is mentioned. In addition, after overlapping the support base material 18 with a resin layer, and the glass substrate 20 with a resin layer as needed, the 1st polyimide resin layer 14a and the 2nd polyimide resin layer 14b are crimped | bonded using a roll or a press. May be. It is preferable because air bubbles mixed between the first polyimide resin layer 14a and the second polyimide resin layer 14b are relatively easily removed by pressure bonding using a roll or a press.

When the first polyimide resin layer 14a and the second polyimide resin layer 14b are pressure-bonded by a vacuum laminating method or a vacuum press method, it is more preferable because it is possible to suppress mixing of bubbles and ensure good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not likely to lead to a distortion defect of the glass substrate 16. Moreover, bubbles are less likely to remain by pressure bonding under vacuum heating.

When laminating the support substrate 18 with a resin layer and the glass substrate 20 with a resin layer, the surface 114a of the first polyimide resin layer 14a and the surface 114b of the second polyimide resin layer 14b are sufficiently washed, It is preferable to laminate in a high environment. The higher the degree of cleanliness, the better the flatness of the glass substrate 16, which is preferable.

In addition, after laminating | stacking the support base material 18 with a resin layer, and the glass substrate 20 with a resin layer, you may perform a pre-annealing process (heating process) as needed. By performing the pre-annealing treatment, the adhesion between the laminated support substrate 18 with a resin layer and the glass substrate 20 with a resin layer can be improved, and an appropriate peel strength can be obtained. In addition, the position of the electronic device member is not easily displaced, and the productivity of the electronic device is improved.
The conditions for the pre-annealing treatment are appropriately selected according to the types of materials used for the first polyimide resin layer 14a and the second polyimide resin layer 14b, but are 200 ° C. or higher (preferably 200 to 400 ° C.). For 5 minutes or more (preferably 5 to 30 minutes).

(Glass laminate)
The glass laminate 10 of the present invention can be used for various applications, for example, manufacturing electronic parts such as a display device panel, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface, which will be described later. The use to do is mentioned. In this application, the glass laminate 10 is often exposed to a high temperature condition (for example, 400 ° C. or more) (for example, 1 hour or more).
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

[Electronic device and manufacturing method thereof]
In this invention, the glass substrate with a member (electronic device) containing a 2nd polyimide resin layer, a glass substrate, and the member for electronic devices is manufactured using the laminated body mentioned above.
The method for producing the electronic device is not particularly limited, but from the viewpoint of excellent productivity of the electronic device, an electronic device member is formed on the glass substrate in the glass laminate to produce a laminate with the electronic device member. A method of separating the obtained laminate with a member for an electronic device into an electronic device and a supporting substrate with a resin layer by using the interface between the first polyimide resin layer and the second polyimide resin layer as a release surface is preferable.
Hereinafter, the step of forming a member for an electronic device on the glass substrate in the glass laminate and manufacturing the laminate with the member for an electronic device is a member forming step, and the laminate with the member for an electronic device is the first polyimide resin layer A process of separating the electronic device and the support substrate with a resin layer using the interface with the second polyimide resin layer as a release surface is referred to as a separation process.
The materials and procedures used in each process are described in detail below.

(Member formation process)
A member formation process is a process of forming the member for electronic devices on the glass substrate 16 in the glass laminated body 10 obtained in the said lamination process. More specifically, as shown in FIG. 2D, the electronic device member 22 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain a laminate 24 with the electronic device member. .
First, the electronic device member 22 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Electronic device components (functional elements))
The electronic device member 22 is a member that is formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 22, a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on its surface (for example, Display member, solar cell member, thin film secondary battery member, electronic component circuit).

For example, as a member for a solar cell, a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a circuit for an electronic component, in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(Process procedure)
The manufacturing method of the laminated body 24 with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of structural member of the member for electronic devices, the 2nd main of the glass substrate 16 of the glass laminated body 10 is used. The electronic device member 22 is formed on the surface 16b.
The electronic device member 22 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as “all members”), but a part of all the members (hereinafter referred to as “parts”). May be referred to as a member. In addition, a glass substrate with a partial member can also be used as a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps.
Moreover, an electronic device can also be manufactured by assembling a laminate with all members, and then peeling the support substrate 18 with a resin layer from the laminate with all members. Further, an electronic device is assembled using two laminates with all members, and then the two support bases 18 with a resin layer are peeled off from the laminate with all members to obtain an electronic device having two glass substrates. It can also be manufactured.

For example, taking the case of manufacturing an OLED as an example, on the surface of the glass laminate 10 opposite to the second polyimide resin layer 14b side of the glass substrate 16 (corresponding to the second main surface 16b of the glass substrate 16). In order to form an organic EL structure, a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, and a back electrode is formed. Various layers are formed and processed, such as sealing with a sealing plate. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.

Further, for example, when manufacturing a TFT-LCD, a resist film is used on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film forming method such as a CVD method or a sputtering method. A TFT forming step of forming a thin film transistor (TFT) by patterning the formed metal film, metal oxide film, etc., and patterning a resist solution on the second main surface 16b of the glass substrate 16 of another glass laminate 10 Various processes such as a CF forming step for forming a color filter (CF) to be used for forming, a laminating step for laminating a laminated body with TFT obtained in the TFT forming step and a laminated body with CF obtained in the CF forming step, etc. Process.

In the TFT formation process and the CF formation process, the TFT and the CF are formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
In addition, before forming TFT and CF, you may wash | clean the 2nd main surface 16b of the glass substrate 16 as needed. As a cleaning method, known dry cleaning or wet cleaning can be used.

In the laminating step, the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other, and are bonded using a sealant (for example, an ultraviolet curable sealant for cell formation). Thereafter, a liquid crystal material is injected into a cell formed by the laminate with TFT and the laminate with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.

(Separation process)
In the separation step, as shown in FIG. 2E, the interface 24 between the first polyimide resin layer 14a and the second polyimide resin layer 14b is peeled off from the laminate 24 with the electronic device member obtained in the member forming step. The surface is separated into a glass substrate 20 with a resin layer (electronic device 26) on which the electronic device member 22 is laminated and a support base material 18 with a resin layer, and the second polyimide resin layer 14b, the glass substrate 16 and the electrons are separated. In this step, a glass substrate with a member (electronic device 26) including the device member 22 is obtained.
When the electronic device member 22 on the glass substrate 16 at the time of peeling is a part of all necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after separation.

The method of peeling the electronic device 26 and the support base material 18 with a resin layer is not specifically limited. Specifically, for example, a sharp blade-like object (claw) is inserted into the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b to give an opportunity for separation, and then water, compressed air, The mixed fluid can be sprayed or peeled off. Preferably, the electronic device member-attached laminate 24 is placed on the surface plate so that the support base material 12 is on the upper side and the electronic device member 22 side is on the lower side, and the electronic device member 22 side is vacuumed on the surface plate. In this state, the blade first enters the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. If it does so, an air layer will be formed in the interface of the 1st polyimide resin layer 14a and the 2nd polyimide resin layer 14b, the air layer will spread over the interface whole surface, and the support substrate 18 with a resin layer can be peeled easily. In addition, when a support base material is laminated | stacked on both surfaces, it peels one by one.
Moreover, the support base material 18 with a resin layer can be laminated | stacked with a new glass substrate, and the glass laminated body 10 of this invention can be manufactured.
In addition, when peeling the electronic device 26 and the support base material 18 with a resin layer, it is preferable to peel while spraying a peeling aid on the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b. The peeling aid intends a solvent such as water described above. Examples of the peeling aid used include water, an organic solvent (for example, ethanol), and a mixture thereof. Further, the second polyimide resin layer formed on the back surface of the peeled electronic device 26 can be removed by a treatment such as washing with water. When high light transmittance such as LCD is required, it is desirable to remove the second polyimide resin layer after peeling.

When the electronic device 26 is separated from the electronic device member-attached laminate 24, the fragments of the first polyimide resin layer 14a and the second polyimide resin layer 14b are removed by controlling the spraying and humidity with an ionizer. 26 can be further suppressed from being electrostatically adsorbed.

The above-described method for manufacturing the electronic device 26 is suitable for manufacturing a small display device used in a mobile terminal such as a mobile phone or a PDA. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like. Basically, the present invention can be applied to both passive drive type and active drive type display devices.

As the electronic device 26 manufactured by the above method, a display device panel having a glass substrate and a display device member, a solar cell having a glass substrate and a solar cell member, and a thin film having a glass substrate and a thin film secondary battery member. Examples thereof include a secondary battery, an electronic component having a glass substrate and an electronic device member. Examples of the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In the following Examples and Comparative Examples, a glass plate made of non-alkali borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.1 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., manufactured by Asahi Glass Co., Ltd.) The name “AN100”) was used. Further, as a supporting base material, a glass plate made of an alkali-free borosilicate glass (length 200 mm, width 200 mm, plate thickness 0.5 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd. )It was used.

<Production Example 1>
Paraphenylenediamine (10.8 g, 0.1 mol) was dissolved in N, N-dimethylacetamide (198.6 g) and stirred at room temperature. To this, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) (29.4 g, 0.1 mmol) was added over 1 minute, and the mixture was stirred at room temperature for 2 hours. -1) and / or a polyamic acid solution (P1) having a solid content concentration of 20% by mass containing a polyamic acid having a repeating unit represented by the formula (2-2) was obtained. When the viscosity of this solution was measured, it was 3000 poise at 20 ° C.
The viscosity is measured by measuring the rotational viscosity at 20 ° C. using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec Co., Ltd.
In the repeating unit represented by the formula (2-1) and / or formula (2-2) contained in the polyamic acid, X is a group represented by (X1), and A is represented by the formula (A1). It was a group.

<Production Example 2>
9,9-bis (4-aminophenyl) fluorene (35 g, 0.1 mol), γ-butyrolactone (69.3 g) as a solvent, and N, N-dimethylacetamide (140 g) were mixed and dissolved. Stir at room temperature. To this was added 1,2,4,5-cyclohexanetetracarboxylic dianhydride (22.5 g, 0.1 mol) over 1 minute, and the mixture was stirred at room temperature for 2 hours to give a polyamic acid having a solid content of 20% by mass. An acid solution Y was obtained. When the viscosity of this solution was measured, it was 3300 poise at 20 ° C.
X in the repeating unit represented by the formula (2-1) and / or formula (2-2) contained in the polyamic acid is a group represented by the formula (X4), and A is a formula (A6). The group represented.

Next, triethylamine (0.51 g, 0.005 mol) was added to the polyamic acid solution Y as an imidization catalyst all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C., refluxed for 5 hours while distilling off the distillate as needed. Amide (130.7 g) was added and cooled with stirring to obtain an alicyclic polyimide resin solution (P2) having a solid concentration of 20% by mass.

<Production Example 3: Production of silicone solution (P3)>
A mixture of 1,1,3,3-tetramethyldisiloxane (5.4 g), tetramethylcyclotetrasiloxane (96.2 g) and octamethylcyclotetrasiloxane (118.6 g) was cooled to 5 ° C. and stirred. Concentrated sulfuric acid (11.0 g) was slowly added while adding water (3.3 g) dropwise over 1 hour. After stirring for 8 hours while maintaining the temperature at 10 to 20 ° C., toluene was added, and water washing and waste acid separation were performed until the siloxane layer became neutral. The neutralized siloxane layer was heated and concentrated under reduced pressure to remove low-boiling fractions such as toluene, and organohydrogensiloxane A with k = 40 and l = 40 in the following formula (3) was obtained.

1,3-divinyl-1,1,3,3-tetramethyldisiloxane (3.7 g), 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (41 0.4g), and potassium hydroxide siliconate is added to octamethylcyclotetrasiloxane (355.9g) in an amount of Si / K = 20000/1 (molar ratio) and allowed to equilibrate at 150 ° C. for 6 hours in a nitrogen atmosphere. Then, 2 mol amount of ethylene chlorohydrin was added to K and neutralized at 120 ° C. for 2 hours. Then, the volatile content was cut by heating and bubbling at 160 ° C. and 666 Pa for 6 hours to obtain an alkenyl group-containing siloxane D having an alkenyl equivalent number La per 0.9 g of La = 0.9 and Mw: 26,000.
Organohydrogensiloxane A and alkenyl group-containing siloxane D were mixed so that the molar ratio (hydrogen atom / alkenyl group) of all alkenyl groups to all hydrogen atoms bonded to silicon atoms was 0.9. To 100 parts by mass of this siloxane mixture, 1 part by mass of a silicon compound having an acetylenically unsaturated group represented by the following formula (4) is mixed, and a platinum-based catalyst is added so that the platinum metal concentration becomes 100 ppm. 5 parts by mass of heptane was added to 100 parts by mass to obtain a silicone solution (P3) containing a crosslinkable organopolysiloxane.
HC≡C—C (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ Formula (4)

<Example 1>
First, a supporting substrate having a thickness of 0.5 mm was cleaned with pure water, and further cleaned by UV cleaning.
Next, N, N-dimethylacetamide was added to the polyamic acid solution (P1) to dilute the solid content concentration of the polyamic acid to 5% by mass to obtain a solution X. The solution X was applied onto the first main surface of the supporting substrate with a spin coater (rotation speed: 2000 rpm, 15 seconds), and a coating film containing polyamic acid was provided on the supporting substrate (coating amount: 2. 0 g / m ² ). The coating amount intends the amount of polyamic acid remaining on the supporting substrate.
The polyamic acid is a resin obtained by reacting the compound represented by the formula (Y1) with the compound represented by the formula (B1).

Next, after heating the coating film in the atmosphere at 60 ° C. for 30 minutes and then at 120 ° C. for 30 minutes, the coating film is further heated at 350 ° C. for 60 minutes to obtain a first polyimide resin layer (thickness: 0.1 μm). Formed. In the formed first polyimide resin layer, a polyimide resin having a repeating unit represented by the following formula (X in formula (1) is a group represented by (X1), A is formula (A1) Consisting of the group represented).

The imidization ratio of the polyimide resin in the first polyimide resin layer was 99.7%. Further, the surface roughness Ra of the surface of the formed first polyimide resin layer was 0.8 nm.
In addition, the measurement of imidation ratio and the measurement of surface roughness Ra were implemented by the above-mentioned method.

Next, the glass substrate was cleaned with pure water, and further cleaned by UV cleaning.
Then, following the same procedure as the method for forming the first polyimide resin layer, the polyamic acid solution (P1) is applied onto the first main surface of the glass substrate with a spin coater (rotation speed: 2000 rpm, 15 seconds), and heated. The treatment was performed to form a second polyimide resin layer (thickness: 5.0 μm, Ra: 1.0 μm).
The imidization ratio of the polyimide resin in the second polyimide resin layer was 99.7%.

Then, the support substrate with a resin layer including the support substrate and the first polyimide resin layer, and the resin including the glass substrate and the second polyimide resin layer so that the first polyimide resin layer and the second polyimide resin layer are in contact with each other. The glass substrate with a layer was bonded together by roll bonding under atmospheric pressure at room temperature to obtain a glass laminate S1.
In the obtained glass laminate S1, the first polyimide resin layer and the second polyimide resin layer were in close contact with each other without generating bubbles, no distortion defects, and good smoothness. In the glass laminate S1, the peel strength at the interface between the first polyimide resin layer and the second polyimide resin layer is the peel strength at the interface between the support substrate and the first polyimide resin layer, and the glass substrate and the second polyimide resin. It was smaller than the peel strength at the interface with the layer.

Next, when the glass laminate S1 is heat-treated at 400 ° C. for 60 minutes in the atmosphere and cooled to room temperature, the glass substrate S1 is separated from the support base material and the glass substrate, or the first polyimide resin layer. No change in appearance such as foaming or whitening of the second polyimide resin layer was observed.
Then, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the first polyimide resin layer and the second polyimide resin layer at one of the four corners of the glass laminate S1 to form a notch for peeling. While forming, the vacuum suction pad is adsorbed on the non-peeling surfaces of the glass substrate and the supporting base material, and water is sprayed on the interface between the first polyimide resin layer and the second polyimide resin layer, while the glass substrate and the supporting base material are sprayed. The glass substrate and the supporting base material were separated without damaging them by applying an external force in the direction of separating them from each other. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation).
In addition, the 1st polyimide resin layer was isolate | separated with the support base material, and the 2nd polyimide resin layer with the glass substrate. Also from the above results, the peel strength at the interface between the first polyimide resin layer and the second polyimide resin layer is the peel strength at the interface between the support substrate and the first polyimide resin layer and between the glass substrate and the second polyimide resin layer. It was confirmed that it was smaller than the peel strength at the interface.

(Measurement of peel strength)
A peel test was performed using the jig described in paragraph 0050 of Japanese Patent No. 5200538. The jig used is shown in FIG. In FIG. 3, the glass laminate S <b> 1 includes a support base 12, a first polyimide resin layer 14 a, a second polyimide resin layer 14 b, and a glass substrate 16.
The glass laminate S1 is cut into a size of 50 mm in length × 50 mm in width, and polycarbonate 60 having a length of 50 mm × width of 50 mm × thickness of 5 mm is formed on the glass (support base material 12 and glass substrate 16) on both sides of the glass laminate S1. Were bonded together with an adhesive for epoxy two-component glass. Further, polycarbonates 70 each having a length of 50 mm, a width of 50 mm, and a thickness of 5 mm were further vertically bonded to the surfaces of both the bonded polycarbonates 60. As shown in FIG. 3, the place where the polycarbonate 70 was bonded was the position of the end of the polycarbonate 60 in the vertical direction and the position parallel to the side of the polycarbonate 60 in the horizontal direction.
The glass laminate S1 bonded with the

polycarbonates

60 and 70 was placed so that the support base 12 was on the lower side. The polycarbonate 70 affixed to the glass substrate 16 side is fixed with a jig, and the polycarbonate 70 affixed to the support base material 12 side is pulled vertically downward at a speed of 300 mm / min. A force of 0.29 kg / cm ² is obtained. The first polyimide resin layer 14a and the second polyimide resin layer 14b were peeled off.

<Example 2>
When forming the first polyimide resin layer, the polyamic acid solution (P1) is used instead of the solution X, and the thickness of the first polyimide resin layer is changed from 0.1 μm to 5.0 μm. In the formation of the layer, the same as in Example 1 except that the solution X was used instead of the polyamic acid solution (P1) and the thickness of the second polyimide resin layer was changed from 5.0 μm to 0.1 μm. By the method, glass laminated body S2 was obtained.
The imidization ratio of the polyimide resin in the first polyimide resin layer and the second polyimide resin layer was 99.5%. Moreover, surface roughness Ra of a 1st polyimide resin layer and a 2nd polyimide resin layer is shown in Table 1 mentioned later.
In the obtained glass laminate S2, the first polyimide resin layer and the second polyimide resin layer were in close contact with each other without generating bubbles, there was no distortion defect, and the smoothness was good. In the glass laminate S2, the peel strength at the interface between the first polyimide resin layer and the second polyimide resin layer is the peel strength at the interface between the support substrate and the first polyimide resin layer, and the glass substrate and the second polyimide resin. It was smaller than the peel strength at the interface with the layer.
Next, when the glass laminate S2 was subjected to the same heat treatment as in Example 1, the support substrate of the glass laminate S2 and the glass substrate were separated, and the first polyimide resin layer and the second polyimide resin layer were foamed. No change in appearance such as whitening was observed.
And about glass laminated body S2, when the support base material and the glass substrate were isolate | separated by the method similar to Example 1, it isolate | separated, without damaging a glass substrate and a support base material.
In addition, the 1st polyimide resin layer was isolate | separated with the support base material, and the 2nd polyimide resin layer with the glass substrate. Also from the above results, the peel strength at the interface between the first polyimide resin layer and the second polyimide resin layer is the peel strength at the interface between the support substrate and the first polyimide resin layer and between the glass substrate and the second polyimide resin layer. It was confirmed that it was smaller than the peel strength at the interface. The above (measurement of peel strength) was carried out using the obtained glass laminate S2. The results are shown in Table 1.

<Example 3>
In the formation of the second polyimide resin layer, the glass laminate S3 was prepared in the same manner as in Example 1 except that the alicyclic polyimide resin solution (P2) was used instead of the polyamic acid solution (P1). Obtained.
In the formed second polyimide resin layer, X in the formula (1) is composed of a group represented by the above formula (X4), and A is a polyimide composed of a group represented by the above formula (A6). Resin was included.
The imidization ratio of the polyimide resin in the first polyimide resin layer and the second polyimide resin layer was 99.5%. Moreover, surface roughness Ra of a 1st polyimide resin layer and a 2nd polyimide resin layer is shown in Table 1 mentioned later.
In the obtained glass laminate S3, the first polyimide resin layer and the second polyimide resin layer were in close contact with each other without generating bubbles, there were no distortion defects, and the smoothness was good. In the glass laminate S3, the peel strength at the interface between the first polyimide resin layer and the second polyimide resin layer is the peel strength at the interface between the support substrate and the first polyimide resin layer and the glass substrate and the second polyimide resin. It was smaller than the peel strength at the interface with the layer.
Next, when the glass laminate S3 was subjected to the same heat treatment as in Example 1, the support substrate of the glass laminate S3 and the glass substrate were separated, and the first polyimide resin layer and the second polyimide resin layer were foamed. No change in appearance such as whitening was observed.
And when glass substrate S3 was isolate | separated from the support base material and the glass substrate by the method similar to Example 1, it isolate | separated, without damaging a glass substrate and a support base material.
In addition, the 1st polyimide resin layer was isolate | separated with the support base material, and the 2nd polyimide resin layer with the glass substrate. Also from the above results, the peel strength at the interface between the first polyimide resin layer and the second polyimide resin layer is the peel strength at the interface between the support substrate and the first polyimide resin layer and between the glass substrate and the second polyimide resin layer. It was confirmed that it was smaller than the peel strength at the interface. The above (measurement of peel strength) was carried out using the obtained glass laminate S3. The results are shown in Table 1.

<Comparative Example 1>
When forming the first polyimide resin layer, the following polyamic acid solution (P4) is used instead of the solution X, and the thickness of the first polyimide resin layer is changed from 0.1 μm to 5.0 μm, When the polyimide resin layer was formed, the solution X was used instead of the polyamic acid solution (P1), and the thickness of the second polyimide resin layer was changed from 5.0 μm to 0.1 μm. In the same manner, an attempt was made to produce the glass laminate C1.
The surface roughness Ra of the obtained first polyimide resin layer was 10.2 nm.
In addition, the following process was implemented as a method of adjusting the said surface roughness Ra.
However, when bonding was performed by roll bonding under atmospheric pressure, the adhesion between the first polyimide resin layer and the second polyimide resin layer was poor, and the desired glass laminate C1 could not be obtained.

(Polyamic acid solution (P4))
Snow Tech (DMAC-ST30, manufactured by Nissan Chemical Industries, average particle size of 80 nm) obtained by dispersing colloidal silica in dimethylacetamide in the polyamic acid solution (P1) obtained in Production Example 1 is a solution having a colloidal deer content. In addition, it added so that it might become 1 mass% with respect to the total mass, and the polyamic acid solution (P4) was obtained.

<Comparative example 2>
Without forming the second polyimide resin layer, the first polyimide resin layer and the glass substrate are laminated according to the same procedure as in Example 2, and the support base, the first polyimide resin layer, and the glass substrate are laminated in this order. A glass laminate C2 was produced.
When the support base material and the glass substrate were separated from the obtained glass laminate C2 in the same manner as in Example 1, it was difficult for the first polyimide resin layer and the glass substrate to be separated. In addition, the above (measurement of peel strength) was carried out using the obtained glass laminate C2. The results are shown in Table 1.

<Comparative Example 3>
Without forming the first polyimide resin layer, the support base material and the second polyimide resin layer are laminated according to the same procedure as in Example 1, and the support base material, the second polyimide resin layer, and the glass substrate are arranged in this order. To produce a glass laminate C3.
When the support base material and the glass substrate were separated from the obtained glass laminate C3 in the same manner as in Example 1, it was difficult for the second polyimide resin layer and the support base material to peel off. The above (measurement of peel strength) was carried out using the obtained glass laminate C3. The results are shown in Table 1.

<Comparative example 4>
In the formation of the first polyimide resin layer, the same method as in Example 1 except that the silicone solution (P3) was used instead of the polyamic acid solution (P1) and the second polyimide resin layer was not formed. And the glass laminated body C4 which has a support base material, a silicone resin layer, and a glass substrate in this order was obtained. In addition, this aspect corresponds to an aspect in which a silicone resin layer is used as the resin layer as shown in Patent Document 1.
About the obtained glass laminated body C4, when the support base material and the glass substrate were separated by the same method as in Example 1, the silicone resin layer and the glass substrate were difficult to peel off, and the silicone resin layer was cohesively broken. In addition to adhering to the glass substrate, the glass substrate was broken. In addition, said (measurement of peeling strength) was implemented using the obtained glass laminated body C4. The results are shown in Table 1.
Moreover, when the glass laminated body C4 was heat-processed at 400 degreeC for 60 minute (s) under air | atmosphere, foaming and whitening of the silicone resin layer were seen.

The results of Examples 1 to 3 and Comparative Examples 1 to 4 are summarized in Table 1 below.
In the “resin type” column in Table 1, P1 means a resin obtained from the solution P1 of Production Example 1, and P2 means a resin obtained from the solution P2 of Production Example 2.

As shown in Table 1, in Examples 1 to 3 using a predetermined resin layer, the adhesion at the time of lamination was excellent, and the resin layer was decomposed even after heat treatment at 400 ° C. for 1 hour. In addition, the peeling of the glass substrate proceeded easily.
On the other hand, in Comparative Example 4 using the silicone resin layer described in Patent Document 1, a desired effect was not obtained.

<Example 4>
In this example, an OLED is manufactured using the glass laminate S1 obtained in Example 1.
First, silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in the glass laminate S1 by plasma CVD. Next, low concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and dehydrogenation treatment is performed in a nitrogen atmosphere. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, then molybdenum is formed by a sputtering method, and etching is performed using a photolithography method. A gate electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after performing a hydrogenation treatment in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Subsequently, by vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine is formed on the second main surface side of the glass substrate, and bis [ (N-naphthyl) -N-phenyl] benzidine, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] to 8-quinolinol aluminum complex (Alq ₃ ) as the light emitting layer A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by a sputtering method. Next, another glass substrate is pasted on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate S1 having an organic EL structure on the glass substrate (hereinafter referred to as panel A) is an electron of the present invention. It is a laminated body with a member for devices.
Subsequently, after the panel A sealing body side is vacuum-adsorbed to the surface plate, a 0.1 mm thick stainless steel material is formed at the interface between the first polyimide resin layer and the second polyimide resin layer at the corner of the panel A. A blade is inserted, and a trigger for peeling is given to the interface between the first polyimide resin layer and the second polyimide resin layer. And after adsorb | sucking the support base material surface of the panel A with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate can be left, and the supporting substrate with the resin layer can be peeled off.
Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method and divided into a plurality of cells, and then the glass substrate on which the organic EL structure is formed and the counter substrate are assembled to form a module. The process is performed to produce an OLED. The OLED obtained in this way does not have a problem in characteristics.

<Example 5>
In this example, an LCD is manufactured using the glass laminate S1 obtained in Example 1.
First, two glass laminates S1-1 and S1-2 are prepared, and silicon nitride, silicon oxide, and amorphous are formed on the second main surface of the glass substrate in one glass laminate S1-1 by plasma CVD. Films are formed in the order of silicon. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, after a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method and a gate insulating film is formed, molybdenum is formed by a sputtering method, and the gate is etched by photolithography. An electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after performing a heat treatment in a hydrogen atmosphere and performing a hydrogenation treatment, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Next, the other glass laminate S1-2 is heat-treated in an air atmosphere. Next, a chromium film is formed on the second main surface of the glass substrate in the glass laminate S1-2 by a sputtering method, and a light-shielding layer is formed by etching using a photolithography method. Next, a color resist is applied to the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by a photolithography method and heat curing. Next, a film of indium tin oxide is formed by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid is applied to the second main surface side of the glass substrate by a die coating method, and columnar spacers are formed by a photolithography method and thermal curing. Next, a polyimide resin solution is applied by a roll coating method, an alignment layer is formed by thermosetting, and rubbing is performed.
Next, a sealing resin liquid is drawn in a frame shape by the dispenser method, and after dropping the liquid crystal in the frame by the dispenser method, two glass sheets S1-1 on which the pixel electrodes are formed are used. The second main surface sides of the glass substrates of the glass laminate S1 are bonded together, and an LCD panel is obtained by ultraviolet curing and thermal curing.

Subsequently, the surface opposite to the first polyimide resin layer side of the supporting substrate of the glass laminate S1-1 is vacuum-adsorbed to a surface plate, and the first polyimide resin layer at the corner of the glass laminate S1-2 A stainless steel knife having a thickness of 0.1 mm is inserted into the interface with the second polyimide resin layer, and a trigger for peeling is applied to the interface between the first polyimide resin layer and the second polyimide resin layer. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while water is being supplied to the separation front while spraying a static elimination fluid from the ionizer toward the formed gap. Then, the suction pad is raised after the second main surface of the supporting base material of the glass laminate S1-2 is sucked by the vacuum suction pad. As a result, only the empty cell of the LCD with the support substrate of the glass laminate S1-1 is left on the surface plate, and the support substrate with the resin layer can be peeled off.

Next, the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-adsorbed on a surface plate, and the first polyimide resin layer and the second polyimide resin layer at the corner of the glass laminate S1-1 A stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the first polyimide resin layer and the second polyimide resin layer. Then, after adsorbing the surface opposite to the first polyimide resin layer side of the support substrate of the glass laminate S1-1 with a vacuum adsorption pad, water is sprayed between the glass substrate and the resin layer while adsorbing. Raise the pad. As a result, only the LCD cell is left on the surface plate, and the supporting substrate with the resin layer can be peeled off. Thus, a plurality of LCD cells composed of a glass substrate having a thickness of 0.1 mm are obtained.

Subsequently, it is divided into a plurality of LCD cells by a cutting process. A step of attaching a polarizing plate to each completed LCD cell is performed, and then a module forming step is performed to obtain an LCD. The LCD obtained in this way does not have a problem in characteristics.

<Example 6>
In this example, an OLED is manufactured using the glass laminate S1 obtained in Example 1.
First, a film of molybdenum is formed on the second main surface of the glass substrate in the glass laminate S1 by a sputtering method, and a gate electrode is formed by etching using a photolithography method. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a gate insulating film, and subsequently an indium gallium zinc oxide film is formed by a sputtering method. An oxide semiconductor layer is formed by etching. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a channel protective layer. Subsequently, a molybdenum film is formed by a sputtering method, and etching is performed using a photolithography method. A source electrode and a drain electrode are formed.
Next, heat treatment is performed in the air. Next, an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a passivation layer. Subsequently, indium tin oxide is formed by a sputtering method, and etching is performed using a photolithography method. A pixel electrode is formed.
Subsequently, by vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine is formed on the second main surface side of the glass substrate, and bis [ (N-naphthyl) -N-phenyl] benzidine, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] to 8-quinolinol aluminum complex (Alq ₃ ) as the light emitting layer A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer are formed in this order, and then aluminum is formed by a sputtering method. Next, another glass substrate is pasted on the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate S1 having an organic EL structure on the glass substrate (hereinafter referred to as panel B) is an electronic device according to the present invention. It is a laminated body with a member for devices (panel for display devices with a supporting substrate).
Subsequently, after the panel B sealing body side is vacuum-adsorbed to the surface plate, a 0.1 mm thick stainless steel is formed at the interface between the first polyimide resin layer and the second polyimide resin layer at the corner of the panel B. A blade is inserted, and a trigger for peeling is given to the interface between the first polyimide resin layer and the second polyimide resin layer. And after adsorb | sucking the support base material surface of the panel B with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate can be left, and the supporting substrate with the resin layer can be peeled off.
Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method and divided into a plurality of cells, and then the glass substrate on which the organic EL structure is formed and the counter substrate are assembled to form a module. The process is performed to produce an OLED. The OLED obtained in this way does not have a problem in characteristics.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2013-269304 filed on Dec. 26, 2013, the contents of which are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10 Glass laminated body 12 Support base material 14a 1st polyimide resin layer 14b 2nd polyimide resin layer 16 Glass substrate 18 Support base material with a resin layer 20 Glass substrate with a resin layer 22 Member for electronic devices 24 Laminated body with members for electronic devices 26 Electronic devices

Claims

A support substrate with a resin layer having a support substrate and a polyimide resin layer (first polyimide resin layer) formed on the support substrate, and a glass substrate and a polyimide resin layer formed on the glass substrate Including a glass substrate with a resin layer having (second polyimide resin layer),
With the support substrate with the resin layer and the resin layer, the first polyimide resin layer in the support substrate with the resin layer and the second polyimide resin layer in the glass substrate with the resin layer are in contact with each other. The glass substrate is laminated,
The surface roughness Ra of the surface of the first polyimide resin layer opposite to the support base and the surface of the second polyimide resin layer opposite to the glass substrate are 2.0 nm or less. A glass laminate.
The polyimide resin comprises a repeating unit having a tetracarboxylic acid residue (X) and a diamine residue (A) represented by the following formula (1), and the tetracarboxylic acid residue: (X) includes at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4), and the residue (A) of the diamine is represented by the following formulas (A1) to (A8): The glass laminated body of Claim 1 containing the at least 1 sort (s) of group chosen from the group which consists of group represented by this.

(In formula (1), X represents a tetracarboxylic acid residue obtained by removing a carboxy group from tetracarboxylic acids, and A represents a diamine residue obtained by removing an amino group from diamines.)
The residue (X) of the tetracarboxylic acid includes at least one of a group represented by the formula (X1) and a group represented by the formula (X4), and the residue (A) of the diamine is represented by the formula (A1) The glass laminated body of Claim 2 containing at least one of group represented by general formula and the group represented by Formula (A6).
The glass laminate according to any one of claims 1 to 3, wherein the supporting substrate is a glass plate.
Forming a member for an electronic device on the surface of the glass substrate in the glass laminate according to any one of claims 1 to 4 to obtain a laminate with the member for an electronic device;
A step of removing the support substrate with the resin layer from the laminate with the electronic device member, and obtaining an electronic device having the second polyimide resin layer, the glass substrate, and the electronic device member. Electronic device manufacturing method.