KR20160102172A - Glass laminate body, and method for manufacturing electronic device - Google Patents

Abstract

The present invention relates to a support substrate having a support substrate and a resin layer having a layer of polyimide resin (a first polyimide resin layer) formed on the support substrate, and a layer of a polyimide resin formed on the glass substrate Wherein the first polyimide resin layer in the supporting substrate having the resin layer and the second polyimide resin layer in the glass substrate having the resin layer are provided in the supporting substrate having the resin layer, Wherein a surface of the first polyimide resin layer on the side opposite to the support substrate side and a surface of the second polyimide resin layer on the side of the second polyimide resin layer are in contact with each other, And the surface roughness Ra of each of the surfaces opposite to the glass substrate side is 2.0 nm or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a glass laminate and a method of manufacturing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass laminate, and more particularly to a glass laminate laminated so that polyimide resin layers are in contact with each other.

The present invention also relates to a method of manufacturing an electronic device using the glass laminate.

BACKGROUND ART In recent years, devices (electronic devices) such as a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED) have been made thinner and lighter in weight. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the manufacturing process of the device.

Therefore, conventionally, a method of forming an electronic device member (for example, a thin film transistor) on a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching treatment has been widely adopted.

However, in this method, for example, when the thickness of one glass substrate is reduced to 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is shaved by the etchant, so productivity and efficiency of use of raw materials It is not preferable. Further, in the method of thinning a glass substrate by chemical etching as described above, when fine scratches are present on the surface of the glass substrate, fine pits (etch pits) are formed starting from scratches by etching, .

In recent years, in order to cope with the above-mentioned problem, a glass laminate in which a thin plate glass substrate and a reinforcing plate are laminated is prepared, an electronic device member such as a display device is formed on a thin plate glass substrate of the glass laminate, A method of separating the reinforcing plate from the reinforcing plate is proposed. For example, in Patent Document 1, the reinforcing plate has a supporting plate and a silicon resin layer fixed on the supporting plate, and the silicon resin layer and the thin plate glass substrate are brought into close contact with each other in a peelable manner. The interface between the silicon resin layer of the glass laminate and the thin plate glass substrate is peeled off and the reinforcing plate separated from the thin plate glass substrate is laminated with a new thin plate glass substrate and can be reused as a glass laminate.

International Publication No. 2007/018028

With respect to the glass laminate including the glass substrate described in Patent Document 1, higher heat resistance has been recently demanded. With the increase and complexity of the electronic device member formed on the glass substrate of the glass laminate, the temperature for forming the electronic device member becomes higher and the time for exposure to the high temperature is also required to be long There are a few cases.

The glass laminate described in Patent Document 1 can be subjected to treatment in air at 350 ° C for 1 hour. However, according to the examination by the inventors of the present invention, when the glass laminate produced according to Patent Document 1 is subjected to the treatment at 400 ° C for 1 hour, when the glass substrate is peeled from the surface of the silicon resin layer, A part of the resin layer may not be peeled off from the surface of the stratum corneum, or a part of the resin of the resin layer may remain on the glass substrate. As a result, the productivity of the electronic device may deteriorate.

Further, under the above-described heating conditions, foaming and whitening due to decomposition of the silicone resin layer occur. If such a decomposition of the resin layer occurs, there is a fear that impurities may be mixed into the electronic device when the electronic device is manufactured on the glass substrate, and as a result, the yield of the electronic device may be deteriorated.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a glass laminate which is excellent in adhesion of a glass substrate before high temperature heat treatment, easily peeled off a glass substrate after high temperature heat treatment, It is intended to provide a sieve.

It is another object of the present invention to provide a method of manufacturing an electronic device using the glass laminate.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems and have completed the present invention.

That is, a first aspect of the present invention is a method of manufacturing a semiconductor device comprising a supporting substrate having a supporting substrate and a resin layer having a layer of polyimide resin (first polyimide resin layer) formed on the supporting substrate, and a supporting substrate having a glass substrate and a polyimide A first polyimide resin layer in a supporting substrate having a resin layer and a glass substrate having a resin layer having a resin layer (second polyimide resin layer), and a second polyimide resin layer in a glass substrate having a resin layer A glass substrate having a resin base layer and a resin base layer having a resin layer is laminated so that the first polyimide resin layer and the second polyimide resin layer are in contact with each other, Is a glass laminate in which the surface roughness Ra of each of the opposite surfaces is 2.0 nm or less.

In the first embodiment, the polyimide resin preferably contains a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the following formula (1) (X) of the acid group further comprises at least one group selected from the group consisting of groups represented by the following formulas (X1) to (X4), wherein the residue (A) And at least one group selected from the group consisting of a group represented by the formula (A8).

In the first embodiment, it is preferable that the residue (X) of the tetracarboxylic acid contains at least one of the group represented by the formula (X1) described later and the group represented by the formula (X4) described later, and the residue ) Contains at least one of a group represented by the formula (A1) described later and a group represented by the formula (A6) described later.

In the first aspect, it is preferable that the supporting substrate is a glass plate.

A second aspect of the present invention is a method for manufacturing a semiconductor device, comprising: a member forming step of forming a member for an electronic device on a surface of a glass substrate in a glass laminate of the first aspect,

A method for manufacturing an electronic device, comprising: a step of removing a supporting substrate having a resin layer from a laminate having an electronic device member, and a separation step of obtaining an electronic device having a second polyimide resin layer, a glass substrate and a member for an electronic device to be.

According to the present invention, it is possible to provide a glass laminate excellent in adhesion of a glass substrate before a high-temperature heat treatment, capable of easily peeling off a glass substrate after a high-temperature heat treatment, and suppressing decomposition of a resin layer.

Further, according to the present invention, a method of manufacturing an electronic device using the glass laminate can be provided.

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

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 various variations and substitutions may be made without departing from the scope of the present invention. Can be added.

As one of the features of the glass laminate of the present invention, a polyimide resin layer (hereinafter simply referred to as a " resin layer ") having a surface with a predetermined surface roughness is disposed on a supporting substrate and a glass substrate, And the like. When these resin layers are laminated, the adhesion between the resin layers is excellent. Further, such a resin layer is excellent in heat resistance at the time of heat treatment, and it is difficult for the peeling strength to rise between the resin layers even after the heat treatment, so that the glass substrate can be easily peeled off.

1 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.

1, the glass laminate 10 comprises a support substrate 12, a glass substrate 16, a first polyimide resin layer 14a (a polyimide resin layer) and a first polyimide resin layer 14b 2 polyimide resin layer 14b (polyimide resin layer). The first polyimide resin layer 14a has one side thereof contacting the supporting substrate 12 and the other side contacting the second polyimide resin layer 14b. In addition, the supporting substrate 12 and the first polyimide resin layer 14a constitute a supporting substrate 18 having a resin layer. The other surface of the second polyimide resin layer 14b is in contact with the first polyimide resin layer 14a while the other surface of the second polyimide resin layer 14b is in contact with the glass substrate 16. [ The glass substrate 16 and the second polyimide resin layer 14b constitute a glass substrate 20 having a resin layer.

The two-layer portion including the supporting substrate 12 and the first polyimide resin layer 14a is a step of reinforcing the glass substrate 20 having the resin layer in the member forming process for producing the electronic device member such as the liquid crystal panel do.

This glass laminate 10 is used until the member forming process 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 a supporting substrate 18 having a resin layer and an electronic device 26, and the supporting substrate 18 having a resin layer constitutes the electronic device 26 It is not the part that does. A glass substrate 20 having a new resin layer is laminated on the supporting substrate 18 having a resin layer and can be reused as a new glass laminate 10. [

The first polyimide resin layer 14a is fixed on the supporting substrate 12 and the first polyimide resin layer 14a is peelably laminated (adhered) to the second polyimide resin layer 14b . In the present invention, there is a difference in peel strength (i.e., stress required for peeling) in the laminate (cohesion) that can be fixed and peelable, and fixing means that peeling strength is high in adhesion. That is, the peel strength of the interface between the first polyimide resin layer 14a and the support substrate 12 is larger than the peel strength between the interface of the first polyimide resin layer 14a and the second polyimide resin layer 14b do. In other words, the peelable lamination (close contact) means that peeling is possible, and peeling is possible 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 is peeled off at the interface between the support substrate 12 and the first polyimide resin layer 14a When the stress in the peeling direction exceeding the strength (x) is applied, the interface between the supporting substrate 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 peel strength y and the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b When the stress in the peeling direction exceeding the peeling strength (y) is applied to the interface, the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b is peeled off. As described above, the peel strength (x) is larger than the peel strength (y).

The second polyimide resin layer 14b is fixed on the glass substrate 16 and the second polyimide resin layer 14b is peelably laminated on the first polyimide resin layer 14a . The peel strength of the interface between the second polyimide resin layer 14b and the glass substrate 16 is larger than the peel strength between the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b do.

Therefore, when stress is applied to the glass laminate 10 in the direction in which the supporting substrate 12 and the glass substrate 16 are peeled off, the glass laminate 10 is bonded to the first polyimide resin layer 14a and the second poly Peeled off at the interface of the mid resin layer 14b and separated into the support substrate 18 having the resin layer and the glass substrate 20 having the resin layer.

The peel strength (x) is preferably sufficiently high as compared with the peel strength (y). The increase in the peel strength x is to increase the adhesion of the first polyimide resin layer 14a to the support substrate 12 and to increase the adhesion strength of the second polyimide resin layer 14b relative to the second polyimide resin layer 14b after the heat treatment Which means that a higher adhesion force can be maintained.

In order to increase the adhesion of the first polyimide resin layer 14a to the supporting substrate 12, a method of forming the first polyimide resin layer 14a on the supporting substrate 12 Preferably, a curable resin to be a polyimide resin containing a repeating unit represented by formula (1) is cured on the supporting substrate 12 by thermal curing to form a predetermined first polyimide resin layer 14a . The first polyimide resin layer 14a bonded to the supporting substrate 12 with high bonding force can be formed by the adhesive force at the time of curing.

As a method for increasing the adhesion of the second polyimide resin layer 14b to the glass substrate 16, for example, as described later, the second polyimide resin layer 14b is formed on the glass substrate 16 (Preferably, a curable resin which is a polyimide resin containing a repeating unit represented by the formula (1) by thermal curing is cured on the glass substrate 16 to form a predetermined second polyimide resin layer 14b )).

On the other hand, it is usual that the bonding force of the first polyimide resin layer 14a after curing to the second polyimide resin layer 14b is lower than the bonding force generated at the time of curing. The first polyimide resin layer 14a and the second polyimide resin layer 14b are in contact with each other to form the support substrate 18 having the resin layer and the glass substrate 20 having the resin layer, The glass laminate 10 satisfying the desired peel strength relationship can be manufactured.

In the following description, first, a description will be given of the case where each layer (supporting substrate 12, glass substrate 16, first polyimide resin layer 14a and second polyimide resin layer 14b) constituting the glass laminate 10 And a method of manufacturing the glass laminate and the electronic device will be described in detail below.

[Supporting substrate]

The supporting substrate 12 supports and reinforces the glass substrate 16 to form the glass substrate 16 at the time of forming the electronic device member in the member forming step (the step of obtaining the laminate having the electronic device member) Thereby preventing deformation, scratches, breakage, and the like.

As the supporting substrate 12, for example, a metal plate such as a glass plate, a plastic plate, an SUS plate, or the like is used. It is preferable that the supporting substrate 12 is formed of a material having a smaller coefficient of linear expansion than that of the glass substrate 16 and that the supporting substrate 12 is formed of the same material as the glass substrate 16 More preferable. That is, the supporting substrate 12 is preferably a glass plate. In particular, the supporting substrate 12 is preferably a glass plate containing the same glass material as the glass substrate 16.

The thickness of the supporting substrate 12 may be thicker or thinner than that of the glass substrate 16. Preferably, 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, (12) is selected. For example, the current member forming process is designed to process a substrate having a thickness of 0.5 mm, and 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, Is 0.1 mm, the thickness of the supporting substrate 12 is 0.4 mm. The thickness of the supporting substrate 12 is preferably 0.2 to 0.5 mm in general, and is preferably thicker than that of the glass substrate 16.

When the supporting substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more because of easy handling and difficulty in breaking. Further, the thickness of the glass plate is preferably 1.0 mm or less because of the reason that the rigidity required to bend properly and not break when peeling after formation of the electronic device member is desired.

The difference in average coefficient of linear expansion between the support substrate 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 200 x 10 < ^-7 > / DEG C or less. If the car is excessively large, there is a possibility that the glass laminate 10 is vigorously bent or the support substrate 12 and the glass substrate 16 are peeled off during heating and cooling in the member forming process. When the material of the supporting substrate 12 is the same as the material of the glass substrate 16, occurrence of such a problem can be suppressed.

[Glass Substrate]

The glass substrate 16 is provided with a second polyimide resin layer 14b on the first main surface 16a and a second main surface 16b on the opposite side of the second polyimide resin layer 14b, Member is installed. That is, the glass substrate 16 is a substrate used for forming an electronic device to be described later.

The type of the glass substrate 16 may be a general one, and examples thereof include glass substrates for display devices such as LCDs and OLEDs. The glass substrate 16 is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. The coefficient of linear expansion specified in JIS R 3102 (revised in 1995) is used as an index of the heat shrinkage ratio.

The contents of JIS R 3102 (revised in 1995) are also incorporated herein by reference.

If the coefficient of linear expansion of the glass substrate 16 is large, the member forming process often involves heat treatment, and various problems are likely to occur. For example, when the thin film transistor (TFT) is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed under cooling is cooled, the positional deviation of the TFT due to heat shrinkage of the glass substrate 16 becomes excessive There is a risk of it becoming dangerous.

The glass substrate 16 is obtained by melting a glass raw material and molding the molten glass into a plate. Such a forming method may be a general method, and for example, a float method, a fusion method, a slot down draw method, a pull call method, a lubrication method, or the like is used. In particular, the glass substrate 16 having a small thickness can be obtained by heating the glass molded into a plate shape at a moldable temperature and thinning it by means of drawing or the like (lead-through method).

The kind of glass of the glass substrate 16 is not particularly limited, but is preferably an alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, or other oxide-based glass mainly containing silicon oxide. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90 mass% in terms of an oxide is preferable.

As the glass of the glass substrate 16, glass suitable for the kind of the electronic device member and the manufacturing process thereof is employed. For example, the glass substrate for a liquid crystal panel includes a glass (alkali-free glass) substantially free of an alkali metal component from the viewpoint that elution of the alkali metal component tends to affect the liquid crystal (however, Ingredients are included). Thus, the glass of the glass substrate 16 is appropriately selected based on the kind of the applied device and the manufacturing process thereof.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.15 mm or less, and further preferably 0.10 mm or less from the viewpoints of reducing the thickness and / or weight of the glass substrate 16. [ When the thickness is 0.3 mm or less, it is possible to impart good flexibility to the glass substrate 16. When the thickness is 0.15 mm or less, the glass substrate 16 can be rolled up.

The thickness of the glass substrate 16 is preferably 0.01 mm or more, because the glass substrate 16 can be easily manufactured and the glass substrate 16 can be easily handled.

Further, the glass substrate 16 may be composed of two or more layers, and in this case, the material forming each layer may be the same kind of 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 are formed so that the positional deviation of the glass substrate 16 until the operation of separating the glass substrate 16 and the supporting substrate 12 is performed And prevents the glass substrate 16 and the like from being broken by the separating operation. 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 of the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b, The peel strength of the interface between the second polyimide resin layer 14b and the glass substrate 16 is lower than the peel strength of the interface between the second polyimide resin layer 14b and the glass substrate 16. [

That is, when the glass substrate 16 and the supporting substrate 12 are separated from each other, they are peeled from the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b, It is difficult to peel off the interface between the first polyimide resin layer 14a and the interface between the glass substrate 16 and the second polyimide resin layer 14b. As a result, the first polyimide resin layer 14a and the second polyimide resin layer 14b are in close contact with each other, but have a surface property capable of being readily peeled off. That is, the first polyimide resin layer 14a and the second polyimide resin layer 14b are bonded to each other to a certain degree of bonding force to prevent displacement of the glass substrate 16, The glass substrate 16 is bonded to the glass substrate 16 with a bonding force so that the glass substrate 16 can be easily peeled off. In the present invention, the property that the surface can easily be peeled off is referred to as peelability. On the other hand, the supporting substrate 12, the first polyimide resin layer 14a, the glass substrate 16, and the second polyimide resin layer 14b are bonded with a bonding force that is relatively difficult to peel off.

It is considered that the first polyimide resin layer 14a and the second polyimide resin layer 14b are bonded with a bonding force due to a weak adhesive force or a van der Waals force.

In some cases, the surface of the first polyimide resin layer 14a and the surface of the second polyimide resin layer 14b before lamination may be laminated by performing a treatment for weakening the bonding force therebetween.

The first polyimide resin layer 14a is bonded to the surface of the supporting substrate 12 with strong bonding force such as an adhesive force or an adhesive force. The improvement in the adhesion between the first polyimide resin layer 14a and the supporting substrate 12 is achieved by forming the first polyimide resin layer 14a on the supporting substrate 12. [ For example, as described later, a curable resin serving as a polyimide resin containing a repeating unit represented by the formula (1) by thermal curing is cured on the surface of the supporting substrate 12 to support the thermally cured polyimide resin And adheres to the surface of the substrate 12 to obtain a high bonding force. Further, a high bonding force can be obtained by bringing the composition containing the polyimide resin into contact with the surface of the supporting substrate 12 and, if necessary, performing the heat treatment to form the first polyimide resin layer 14a. The surface of the supporting substrate 12 and the first polyimide resin layer 14a are subjected to a treatment (for example, a treatment using a coupling agent) that generates a strong bonding force between the surface of the supporting substrate 12 and the first polyimide resin layer 14a, 1 bonding strength between the polyimide resin layers 14a.

The second polyimide resin layer 14b is also bonded to the surface of the glass substrate 16 with strong bonding force such as adhesive force or 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 is set such that at least one of the first polyimide resin layer 14a and the second polyimide resin layer 14b It is preferably 1 占 퐉 or more from the viewpoint of allowing the blade to penetrate the blade to generate a peeling starting point, and more preferably 2 占 퐉 or more and more preferably 4 占 퐉 or more from the viewpoint of releasability. The upper limit is not particularly limited, but is preferably 100 mu m or less.

When the thickness of one of the first polyimide resin layer 14a and the second polyimide resin layer 14b is within the above range, the thickness of the other polyimide resin layer 14a and the second polyimide resin layer 14b is not particularly limited and is preferably 0.1 to 100 占 퐉, for example More preferably 0.5 to 50 占 퐉, and still more preferably 1 to 20 占 퐉. When the thicknesses of the first polyimide resin layer 14a and the second polyimide resin layer 14b are in this range, air bubbles are formed between the first polyimide resin layer 14a and the second polyimide resin layer 14b The occurrence of distortion defects in the glass substrate 16 can be suppressed even when foreign objects are present.

The thickness is intended to mean the average thickness, and the thickness of any five points of the first polyimide resin layer 14a (or the second polyimide resin layer 14b) is measured and arithmetically averaged.

The surface 114a of the first polyimide resin layer 14a opposite to the side of the supporting substrate 12 and the side 114b of the surface 114b of the second polyimide resin layer 14b opposite to the side of the glass substrate 16 The surface roughness Ra is 2.0 nm or less and preferably 1.5 nm or less and more preferably 1.0 nm or less in view of better adhesion between the support substrate 18 having the resin layer and the glass substrate 20 having the resin layer Do. The lower limit is not particularly limited, but is preferably 0 nm.

When the surface roughness Ra is larger than 2.0 nm, adhesion between the first polyimide resin layer 14a and the second polyimide resin layer 14b is deteriorated.

In general, a method of forming a polyimide resin into a layer includes a method of producing a thermoplastic polyimide resin followed by extrusion molding or a method of applying a solution containing a curable resin to be a polyimide resin by thermosetting onto a substrate, There is a method of curing on the surface. In the present invention, by forming the resin layer by the latter method, a resin layer having a surface roughness Ra within the above range is easily obtained.

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 Modified Flatten order-2, Planefit order-2) Measurement method of surface roughness of fine ceramics thin film by microscope JIS R 1683: 2007 reference).

The contents of JIS R 1683: 2007 are also incorporated herein by reference.

The reasons for the increase in Ra are (1) inherent type (additive), (2) surface roughening due to foaming, and (3) environmental factors (foreign matter). As a countermeasure to the method (1), it is preferable to use a glass substrate having a smooth surface as a prerequisite, and not to use an actinic agent or filler for the coating liquid. The coating method is not particularly limited, but it is preferable to coat it using a die coater, for example. When the drying of the solvent becomes excessively rapid, foaming occurs, and the problem (2) arises. As a countermeasure therefor, a surface smooth film is obtained by optimizing the drying temperature and time. In the examples described below, pre-drying was performed on a hot plate at 80 DEG C for 30 minutes and at 120 DEG C for 30 minutes, and then heated at 350 DEG C for 1 hour in a hot-air drying furnace. Further, the heating conditions are not limited to the above process. In addition, since the foreign object may cause surface roughness, manufacturing in a clean room is suitable as a measure against (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 may be a structure in which the residues X of the tetracarboxylic acids represented by the following formula (1) And a repeating unit having a residue (A) of a diamine. The polyimide resin preferably contains the repeating unit represented by the formula (1) as a main component (preferably 95 mol% or more based on the total repeating units), but other repeating units (for example, Or a repeating unit represented by the following formula (2-1) or (2-2)).

Further, the residue (X) of the tetracarboxylic acid is intended to mean a tetracarboxylic acid residue excluding the carboxyl group from the tetracarboxylic acid, and the residue (A) of the diamine is intended to be a diamine residue excluding the amino group from the diamine.

In the formula (1), X represents a tetracarboxylic acid residue excluding a carboxy group from a tetracarboxylic acid, and A represents a diamine residue excluding an amino group from a diamine.

X in the formula (1) represents a tetracarboxylic acid residue excluding a carboxyl group from a tetracarboxylic acid and includes at least one kind of group selected from the group consisting of the following formulas (X1) to (X4) desirable. Among them, the peelability of 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 are more excellent (Preferably 80 to 100 mol%) of the total number of X in the formulas (X1) to (X1) to (X1) to And at least one group selected from the group consisting of a group represented by the following formula (X4). It is more preferable that the substantially total number (100 mol%) of the total number of X includes at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4).

It is preferable that A represents a diamine residue other than the amino group from the diamines and includes at least one group selected from the group consisting of the following groups represented by the following formulas (A1) to (A8). Among them, it is preferable that 50 mol% or more (preferably 80 to 100 mol%) of the total number of A is the group represented by the following formulas (A1) to (A8) And at least one group selected from the group consisting of It is more preferable that the substantially total number (100 mol%) of the total number of A includes at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

It is preferable that 80 to 100 mol% of the total number of X include at least one kind of group selected from the group consisting of the groups represented by the following formulas (X1) to (X4) in view of better effects of the present invention , And it is also preferred that 80 to 100 mol% of the total number of A contains at least one group selected from the group consisting of the following groups represented by the following formulas (A1) to (A8) (100 mol%) of the total number of A atoms and at least one group selected from the group consisting of the groups represented by the following formulas (X1) to (X4) More preferably at least one group selected from the group consisting of the groups represented by the following formulas (A1) to (A8).

Among them, a group represented by the formula (X1) and a group represented by the formula (X4) are preferable, and a group represented by the formula (X1) is more preferable for X from the viewpoint that the effect of the present invention is better.

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 for the A from the viewpoint of the better effect of the present invention.

As a polyimide resin containing a suitable combination of a group represented by the formulas (X1) to (X4) and a group represented by the formulas (A1) to (A8), X is a group represented by the formula (X1) And polyimide resin 2 in which X is a group represented by the formula (X4) and A is a group represented by the formula (A6). In the case of polyimide resin 1, heat resistance is better. In the case of polyimide resin 2, it is preferable from the viewpoint of colorless transparency.

The repeating number (n) of the repeating unit represented by the formula (1) in the polyimide resin is not particularly limited, but is preferably an integer of 2 or more, and the number of the first polyimide resin layer 14a and the number of the second polyimide From the viewpoint of the heat resistance of the paper layer 14b and the film formability of the coating film, 10 to 10000 is preferable, and 15 to 1000 is more preferable.

The polyimide resin may contain at least one member selected from the group consisting of the following groups as the residue (X) of the tetracarboxylic acid within a range that does not impair the heat resistance. In addition, two or more of the groups illustrated below may be included.

The polyimide resin may contain at least one member selected from the group consisting of the groups shown below as residues (A) of the diamines within a range that does not impair the heat resistance. In addition, two or more of the 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 from the viewpoint of the effect of the present invention being more excellent, , Preferably 50 to 100 mass%, more preferably 75 to 100 mass%, still more preferably 90 to 100 mass%.

The first polyimide resin layer 14a and the second polyimide resin layer 14b may contain components other than the polyimide resin (for example, a filler that does not hinder heat resistance) if necessary.

Examples of the filler that does not inhibit heat resistance include fibrous fillers and fibrous fillers such as flake, scaly, granular, irregular, and crushed products. Specific examples thereof include glass fibers, PAN fibers, Carbon fiber, stainless steel fiber, metal fiber such as aluminum fiber or brass fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker , Calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate , Graphite, metal powder, metal flake, metal ribbon, metal oxide, carbon powder, graphite, carbon flake, scaly car And the like, and carbon nanotubes. Specific examples of metal species of metal powder, metal flake, metal ribbon and metal oxide include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chrome and tin.

The first polyimide resin layer 14a and the second polyimide resin layer 14b are preferably polyimide resin layers formed by heat-treating a layer of a curable resin that becomes a polyimide resin by thermal curing , And further a layer of a curable resin which is a polyimide resin containing a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the formula (1) Is more preferably a layer of a polyimide resin formed by performing the above-mentioned process. The heat treatment may be performed stepwise by changing the temperature.

The production method of the first polyimide resin layer 14a and the second polyimide resin layer 14b will be described in detail in the production method of the later-described glass laminate.

[Production method of glass laminate]

As a method for producing the glass laminate 10 of the present invention, for example, a curable resin to be described later is used while a first polyimide resin layer 14a is formed on a supporting substrate 12 by using a curable resin to be described later A second polyimide resin layer 14b is formed on the glass substrate 16 and thereafter the first polyimide resin layer 14a and the second polyimide resin layer 14b are brought into contact with each other to form a resin layer A supporting substrate 18 and a glass substrate 20 having a resin layer are laminated to produce a glass laminate 10. [

When the curable resin is cured on the surface of the supporting substrate 12, the first polyimide resin layer 14a and the supporting substrate 12 are bonded to each other by the interaction with the surface of the supporting substrate 12 during the curing reaction, The peel strength between the polyimide resin layer 14a and the surface of the supporting substrate 12 is considered to be high. This also applies to the case where the curable resin is cured on the surface of the glass substrate 16.

Hereinafter, the step of forming the first polyimide resin layer 14a on the supporting substrate 12 by using the curable resin to be described later is performed on the glass substrate 16 using the first resin layer forming step and the curable resin layer described later The second polyimide resin layer 14b is formed by a second resin layer forming step, a glass substrate 20 having a supporting substrate 18 having a resin layer and a resin layer is laminated to form the glass laminate 10 The step of obtaining is called a laminating step, and the procedure of each step will be described in detail.

In the following, the mode of using the curable resin is described in detail, but the present invention is not limited thereto. A predetermined polyimide resin may be brought into contact with the support substrate 12 (or the glass substrate 16) The first polyimide resin layer 14a (or the second polyimide resin layer 14b) may be formed. Particularly, in the case of using a solution in which a polyimide resin is dissolved in a solvent, it is preferable to conduct a heat treatment in order to volatilize the solvent. A laminating step to be described later may be performed using a glass substrate having a resin substrate and a resin substrate having a resin layer obtained by the above process.

(First resin layer forming step)

The first resin layer forming step is a step of obtaining a polyimide resin layer by applying heat treatment to a layer of a curable resin which is formed on a supporting substrate and becomes a polyimide resin by thermal curing. In addition, as described above, the polyimide resin preferably contains a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the formula (1) It is preferable that the residue (X) of the 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) And at least one group selected from the group consisting of a group represented by the formula (A8). As shown in Fig. 2A, the first polyimide resin layer 14a is formed on at least one surface of the supporting substrate 12 in the process.

Hereinafter, the resin layer forming step will be described by dividing it into the following two steps.

Step (1): A step of applying a curable resin, which is a polyimide resin containing the repeating unit represented by the above formula (1), onto the supporting substrate 12 by thermal curing to obtain a coated film

Step (2): Step of forming a first polyimide resin layer 14a by applying a heat treatment to the coated film

Hereinafter, the procedure of each step will be described in detail.

(Step (1): Coating film forming step)

The step (1) is a step of applying a curable resin, which is a polyimide resin having a repeating unit represented by the above formula (1), to the supporting substrate 12 by thermosetting to obtain a coated film.

The curable resin preferably contains a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine, and it is preferable that at least a part of the tetracarboxylic acid dianhydride is a compound represented by the following formulas (Y1) to (Y4) , And at least one kind of diamines selected from the group consisting of at least one kind of diamine selected from the group consisting of compounds represented by the following formulas (B1) to (B8) .

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

The reaction conditions of the tetracarboxylic dianhydride and the diamines are not particularly limited and the reaction is preferably carried out at -30 to 70 ° C in view of the efficient synthesis of the polyamic acid, .

The mixing ratio of the tetracarboxylic dianhydride and the diamine is not particularly limited, but it is preferable that the tetracarboxylic dianhydride is used in an amount of 0.66 to 1.5 moles, more preferably 0.9 to 1.1 moles, Preferably 0.97 to 1.03 mol, per mole of the reaction product.

In the reaction of the tetracarboxylic dianhydride and the diamine, an organic solvent may be used if necessary. The kind of the organic solvent to be used is not particularly limited, and examples thereof include N, N-dimethylacetamide, N, N, N-diethylformamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p- chlorophenol, Diglyme, triglyme, tetraglyme, dioxane, gamma -butyrolactone, dioxolane, cyclohexanone, cyclopentanone, and the like may be used, and two or more of them may be used in combination.

In the above reaction, tetracarboxylic acid dianhydride other than the tetracarboxylic acid dianhydride selected from the group consisting of the compounds represented by the above-mentioned formulas (Y1) to (Y4) may be used together if necessary.

In the above reaction, diamines other than the diamines selected from the group consisting of the compounds represented by the above-mentioned formulas (B1) to (B8) may be used together if necessary.

The curable resin to be used in the present step may contain a tetracarboxylic acid dianhydride or a diamine which can react with a polyamic acid in addition to the polyamic acid obtained by reacting the tetracarboxylic dianhydride with a diamine . It is possible to add a tetracarboxylic acid dianhydride or a diamine in addition to the polyamic acid to convert at least two polyamic acid molecules having a repeating unit represented by the formula (2-1) or (2-2) into a tetracarboxylic acid dianhydride Water or a diamine.

When an amino group is present at the terminal of the polyamic acid, a tetracarboxylic acid dianhydride may be added, or may be added so that the carboxyl group is 0.9 to 1.1 moles per mole of the polyamic acid. When a carboxyl group is present at the terminal of the polyamic acid, a diamine may be added, or the amino group may be added in an amount of 0.9 to 1.1 moles per mole of the polyamic acid. When the polyamide acid has a carboxyl group at the terminal thereof, the acid terminal may be obtained by ring opening the terminal acid anhydride group by adding water or an optional alcohol.

The tetracarboxylic dianhydride to be added later is more preferably a compound represented by the formula (Y1) to (Y4). The diamines to be added afterward are preferably diamines having aromatic rings, more preferably compounds represented by the formulas (B1) to (B8).

When the tetracarboxylic acid dianhydrides or diamines are added later, the polymerization degree (n) of the polyamic acid having the repeating unit represented by the formula (2-1) or (2-2) is preferably 1 to 20 . When the degree of polymerization (n) is within this range, the solution of the curable resin can be made to have a low viscosity even if the polyamic acid concentration in the solution of the curable resin is 30 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 in view of the solubility of the polyamic acid. As the organic solvent to be used, an organic solvent used in the above-mentioned reaction can be mentioned.

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. Generally, Is preferably 5 to 95 mass%, more preferably 10 to 90 mass%.

If necessary, a dehydrating agent or a dehydrating ring-closing catalyst may be used together to promote dehydration ring closure of the polyamic acid. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used.

In addition, a filler that does not impair the above-described heat resistance may be included.

The method of applying the curable resin (or the curable resin solution) on the surface of the support substrate 12 is not particularly limited and a known method can be used. Examples of the coating method include a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method and a gravure coating method.

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 above-described desired thickness can be obtained.

(Process (2): heat treatment process)

Step (2) is a step of forming a first polyimide resin layer 14a by applying a heat treatment to the coated film. By carrying out this step, for example, the cyclization reaction of the polyamic acid contained in the curable resin proceeds to form a desired resin layer.

The method of the heat treatment is not particularly limited, and a well-known method (for example, a method of heating and heating a supporting substrate having a coating film in a heating oven) is suitably used.

Although the heating temperature is not particularly limited, it is preferably 250 deg. C or more and 500 deg. C or less, more preferably 300 deg. C to 450 deg. C from the standpoint of lowering the residual solvent ratio and further increasing the imidization rate, More preferable.

The heating time is not particularly limited, and the optimum time is appropriately selected depending on the structure of the curable resin used. However, since the residual solvent ratio is lowered and the imidization rate is further increased, the effect of the present invention is more excellent , Preferably 15 to 120 minutes, and more preferably 30 to 60 minutes.

The atmosphere of heating is not particularly limited, and is carried out, for example, under the atmosphere, under vacuum, or under an inert gas.

Further, the heat treatment may be carried out stepwise at different temperatures.

Also, before the treatment at the heating temperature, a drying heat treatment for removing the volatile component (solvent) in the coating film may be carried out if necessary. The temperature condition of the dry heat treatment is not particularly limited, but heat treatment at 40 캜 to 200 캜 is preferable in that the effect of the present invention is better. The drying time is not particularly limited and is preferably 15 to 120 minutes, and more preferably 30 to 60 minutes, in that the effect of the present invention is better. Further, the dry heat treatment may be carried out stepwise at different temperatures.

Therefore, one of the preferable forms of the present step (2) is a method in which after the drying heat treatment at the temperature is performed, the heat treatment at 250 DEG C or higher and 500 DEG C or lower is carried out again.

By going through the above step (2), the first polyimide resin layer 14a including the polyimide resin is formed.

The imidization rate of the polyimide resin is not particularly limited, but is preferably 99.0% or more, and more preferably 99.5% or more, from the viewpoint of the effect of the present invention being more excellent.

The measurement method of the imidization rate is as follows. When the curable resin is heated at 350 DEG C for 2 hours in a nitrogen atmosphere, the imidization rate is set to 100%, and the peak intensity before and after the heat treatment in the IR spectrum of the curable resin (for example, Peak: about 1500 cm ^-1 ), the imidation rate is obtained by the intensity ratio of the peak intensity from the imidecarbonyl group: about 1780 cm ^-1 .

(Second resin layer forming step)

The second resin layer forming step is a step of forming a layer of the second polyimide resin on the glass substrate by applying heat treatment to the layer of the curable resin that becomes the polyimide resin by thermal curing. As described above, it is preferable that the polyimide resin contains a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the formula (1). In this step, by performing the same procedure (coating film forming step and heat treatment step) as the above-mentioned first resin layer forming step, as shown in FIG. 2 (B) The second polyimide resin layer 14b is formed.

(Lamination step)

In the laminating step, the supporting substrate 18 having the resin layer obtained in the above-mentioned first resin layer forming step and the glass substrate 20 having the resin layer obtained in the second resin layer forming step are laminated and the supporting substrate 12 ), A first polyimide resin layer 14a, a second polyimide resin layer 14b, and a glass substrate 16 in this order. More specifically, as shown in Fig. 2C, the surface 114a of the first polyimide resin layer 14a opposite to the side of the supporting substrate 12 and the surface 114a of the second polyimide resin layer The first polyimide resin layer 14a and the second polyimide resin layer 14b are laminated with the surface 114b on the opposite side of the glass substrate 16 side of the first polyimide resin layer 14a and the second polyimide resin layer 14b as the lamination surface, 10).

The method of laminating the supporting substrate 18 having a resin layer and the glass substrate 20 having a resin layer is not particularly limited and a known method can be employed.

For example, the second polyimide resin layer 14b in the glass substrate 20 having the resin layer on the surface of the first polyimide resin layer 14a in the supporting substrate 18 having the resin layer under an atmospheric pressure environment is superposed . After the support substrate 18 having the resin layer and the glass substrate 20 having the resin layer are stacked as required, the first polyimide resin layer 14a and the second polyimide resin layer 14b are formed using a roll or a press, (14b) may be pressed. It is preferable that bubbles mixed in between the first polyimide resin layer 14a and the second polyimide resin layer 14b are relatively easily removed by pressing by roll or press.

The first polyimide resin layer 14a and the second polyimide resin layer 14b are pressed together by a vacuum laminating method or a vacuum press method so that mixing of bubbles is suppressed and good adhesion is ensured. Even when minute bubbles remain, the bubbles do not grow due to heating, which makes it difficult to cause distortion defects in the glass substrate 16. Further, by pressing under vacuum heating, bubbles are less likely to remain.

The surface 114a of the first polyimide resin layer 14a and the surface of the second polyimide resin layer 14b on the surface of the second polyimide resin layer 14b are laminated on the support substrate 18 having the resin layer and the glass substrate 20 having the resin layer, It is preferable to thoroughly clean the resin layer 114b and laminate it in an environment with high cleanliness. The higher the cleanliness, the better the flatness of the glass substrate 16 is.

Further, after the support substrate 18 having a resin layer and the glass substrate 20 having a resin layer are laminated, a pre-annealing treatment (heat treatment) may be carried out if necessary. By performing the pre-annealing process, adhesion between the support substrate 18 having a laminated resin layer and the glass substrate 20 having a resin layer can be improved, and an appropriate peel strength can be obtained. In the member forming process The positional deviation and the like of the electronic device member are less likely to occur, and the productivity of the electronic device is improved.

The conditions of the pre-annealing treatment are appropriately selected in accordance with the kind of the materials of the first polyimide resin layer 14a and the second polyimide resin layer 14b to be used, Deg.] C to 400 [deg.] C) for 5 minutes or longer (preferably 5 to 30 minutes).

(Glass laminate)

The glass laminate 10 of the present invention can be used for various purposes, for example, for the purpose of producing electronic components such as display panel, PV, thin-film secondary battery, semiconductor wafer with a circuit formed on the surface, etc. . Further, in the intended use, the glass laminate 10 is often exposed to high temperature conditions (for example, 400 DEG C or more) (for example, 1 hour or more).

Here, the display device panel includes an LCD, an OLED, an electronic paper, a plasma display panel, a field emission panel, a quantum dot LED panel, a MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.

[Electronic device and manufacturing method thereof]

In the present invention, a glass substrate (electronic device) having a second polyimide resin layer, a glass substrate, and a member including a member for an electronic device is manufactured using the above-described laminate.

The production method of the electronic device is not particularly limited, but from the viewpoint of excellent productivity of the electronic device, the electronic device member is formed on the glass substrate in the glass laminate to produce a laminate having the electronic device member, It is preferable that the laminate having a member for an electronic device is separated into a supporting substrate having an electronic device and a resin layer with the interface between the first polyimide resin layer and the second polyimide resin layer being peeled off.

Hereinafter, a step of forming a member for an electronic device on a glass substrate in the glass laminate to produce a laminate having an electronic device member is referred to as a member forming step, a step of forming a laminate having a member for an electronic device on the first polyimide resin layer The step of separating the second polyimide resin layer into a supporting substrate having an electronic device and a resin layer as a peeled interface is referred to as a separation step.

Hereinafter, materials and procedures used in each step will be described in detail.

(Member forming process)

The member forming step is a step of forming an electronic device member on the glass substrate 16 in the glass laminate 10 obtained in the laminating step. More specifically, the electronic device member 22 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 as shown in Fig. 2 (D) To obtain a layered product (24).

First, the electronic device member 22 used in this process will be described in detail and the procedure of the subsequent process will be described in detail.

(Member for electronic device (functional element))

The member 22 for the electronic device is a member formed on the glass substrate 16 in the glass laminate 10 and constituting at least a part of the electronic device. More specifically, as the member 22 for the electronic device, a member used for a display device panel, a solar cell, a thin-film secondary battery, or an electronic part such as a semiconductor wafer on which a circuit is formed (for example, Members for solar cells, members for thin film secondary batteries, circuits for electronic parts).

For example, as a member for a solar cell, a transparent electrode such as tin oxide of a positive electrode in a silicon type, a silicon layer and a metal of a negative electrode represented by a p layer / an i layer / an n layer, , A quantum dot type, and the like.

Examples of members for a thin film secondary battery include 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, and the like in the lithium ion type. Various members corresponding to nickel-nickel-plated, polymer-type, ceramics-electrolyte-type, and the like.

Examples of the circuit for electronic parts include a metal of a conductive portion, silicon oxide of silicon and silicon nitride in a CCD or a CMOS, and various sensors such as a pressure sensor and an acceleration sensor, a rigid printed substrate, a flexible printed substrate, Various members corresponding to substrates and the like.

(Process procedure)

The method of manufacturing the laminate 24 having the above-described electronic device member is not particularly limited, and the glass substrate 16 of the glass laminate 10 may be formed by a conventionally known method depending on the type of the constituent member of the electronic device member The electronic device member 22 is formed on the second main surface 16b of the electronic device.

It should be noted that the electronic device member 22 is not a whole of a member finally formed on the second main surface 16b of the glass substrate 16 Quot; partial member "). Further, the glass substrate having the partial members may be a glass substrate (corresponding to an electronic device described later) having an entire member in a subsequent step.

Further, an electronic device may be manufactured by assembling a laminate having an entire member, and thereafter peeling the support base material 18 having a resin layer from the laminate having the entire member. Further, the electronic device is assembled by using two laminated members having the entire member, and then the supporting substrate 18 having two resin layers is peeled from the laminated member having the entire member, May be manufactured.

For example, in the case of manufacturing an OLED, the surface of the glass substrate 16 of the glass laminate 10 on the side opposite to the second polyimide resin layer 14b side (the surface of the glass substrate 16 A hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and the like are deposited on the surface on which the transparent electrode is formed to form the organic EL structure on the second main surface 16b) And the formation and treatment of various layers such as sealing with a sealing plate are performed. Specific examples of such layer formation and treatment include film forming treatment, vapor deposition treatment, adhesion treatment of a sealing plate, and the like.

For example, in the case of manufacturing a TFT-LCD, a resist solution is used on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film formation method such as a CVD method and a sputtering method A TFT forming step of forming a thin film transistor (TFT) by forming a pattern on a metal film and a metal oxide film to be formed on the first main surface 16b of the glass laminate 10; And a bonding step of laminating a laminate having CF obtained in the laminate having the TFT obtained in the TFT forming step and CF obtained in the TFT forming step.

In the TFT forming step and the CF forming step, a TFT or CF is formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique or an etching technique. At this time, a resist solution is used as a coating liquid for pattern formation.

Further, the second main surface 16b of the glass substrate 16 may be cleaned before forming the TFT or the CF, if necessary. As the cleaning method, well-known dry cleaning or wet cleaning can be used.

In the bonding step, the thin film transistor formation surface of the laminate having the TFT and the color filter formation surface of the CF laminate are opposed to each other and are bonded together using a sealing agent (for example, a UV-curable sealing agent for forming a cell). Thereafter, the liquid crystal material is injected into the cell formed of the laminate having the TFT and the CF laminate. As a method of injecting the liquid crystal material, for example, there are a reduced pressure injection method and a dropping injection method.

(Separation step)

2 (E), the laminate 24 having the electronic device member obtained in the member forming step is laminated on the first polyimide resin layer 14a and the second polyimide resin layer 14a, (Electronic device 26) having a resin layer in which the electronic device member 22 is laminated and the supporting substrate 18 having the resin layer are separated (Electronic device 26) having a member including the second polyimide resin layer 14b, the glass substrate 16, and the electronic 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 may be formed on the glass substrate 16 after the detachment.

The method for peeling the electronic device 26 and the support base material 18 having the resin layer is not particularly limited. Concretely, for example, a sharp knife-like nail (nail) is inserted into the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b to give a moment of peeling, The mixed fluid of compressed air can be injected or separated. Preferably, the support member 12 of the layered product 24 having the electronic device member is disposed on the upper surface side and the electronic device member 22 side is disposed on the lower surface side, and the electronic device member 22 side In this state, the blade is first introduced into the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b. Thereafter, the support substrate 12 side is adsorbed by a plurality of vacuum adsorption pads, and the vacuum adsorption pads are raised in order from the vicinity of the position where the blade is inserted. An air layer is formed on the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b and the air layer is expanded on the entire surface of the interface so that the supporting substrate 18 having the resin layer can be easily . In the case where the supporting base material is laminated on both surfaces, the peeling is carried out successively.

Further, the supporting substrate 18 having a resin layer can be laminated with a new glass substrate to produce the glass laminate 10 of the present invention.

When the electronic device 26 and the supporting substrate 18 having the resin layer are peeled off, the peeling aid is sprayed onto the interface between the first polyimide resin layer 14a and the second polyimide resin layer 14b . The release aid means a solvent such as the above-mentioned water. Examples of the release agent to be used include water, an organic solvent (for example, ethanol), etc., or a mixture thereof. In addition, the second polyimide resin layer formed on the back surface of the peeled electronic device 26 can be removed by a process such as washing with water. When a high light transmittance such as an LCD is required, it is preferable to remove the second polyimide resin layer after peeling off.

When the electronic device 26 is separated from the laminate 24 having the electronic device member, the first polyimide resin layer 14a and the second polyimide It is possible to further suppress the electrostatic adsorption of the pieces of the resin layer 14b to the electronic device 26. [

The above-described manufacturing method of the electronic device 26 is suitable for manufacturing a small-sized display device used in a mobile terminal such as a cellular phone or a PDA. The display device is mainly an LCD or an OLED, and examples of the LCD include TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type and the like. It can basically be applied to any of passive drive type and active drive type display devices.

As the electronic device 26 manufactured by the above method, there can be used a display panel having a glass substrate and a display device member, a solar cell having a glass substrate and a solar cell member, a thin film secondary member having a glass substrate and a member for a thin film secondary battery A battery, an electronic part having a glass substrate and a member for an electronic device, and the like. The display panel includes a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.

Example

Hereinafter, the present invention will be described in detail by way of examples and the like, but the present invention is not limited by these examples.

In the following Examples and Comparative Examples, a glass plate (200 mm in length, 200 mm in width, 0.1 mm in plate thickness, and a linear expansion coefficient of 38 x 10 < ^-7 > / deg. &Quot; AN100 "). As a supporting substrate, a glass plate (200 mm in length, 200 mm in width, 0.5 mm in plate thickness, and a linear expansion coefficient of 38 x 10 < ^-7 > / ° C, trade name "AN100" manufactured by Asahi Glass Co., Used.

≪ Preparation Example 1 &

Para-phenylenediamine (10.8 g, 0.1 mole) was dissolved in N, N-dimethylacetamide (198.6 g), and the mixture was stirred at room temperature. To this solution, 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, A polyamic acid solution (P1) having a solid content concentration of 20 mass% comprising a polyamic acid having a repeating unit represented by the formula (1) and / or the formula (2-2) was obtained. The viscosity of this solution was measured and found to be 3000 poises at 20 ° C.

The viscosity was measured using a DVL-BII type viscometer (B-type viscometer) manufactured by Tokimec Co., Ltd., and the rotational viscosity at 20 캜 was measured.

X in the repeating unit represented by the formula (2-1) and / or the formula (2-2) contained in the polyamic acid is a group represented by (X1) and A is a group represented by the formula (A1) .

≪ Preparation Example 2 &

(35 g, 0.1 mol) of 9,9-bis (4-aminophenyl) fluorene, 69.3 g of γ-butyrolactone as a solvent and 140 g of N, N-dimethylacetamide were mixed and dissolved, Lt; / RTI > Cyclohexanetetracarboxylic dianhydride (22.5 g, 0.1 mole) was added thereto over 1 minute, and the mixture was stirred at room temperature for 2 hours to obtain a polyamic acid solution having a solid concentration of 20% by mass Y was obtained. The viscosity of this solution was measured and found to be 3300 poise at 20 占 폚.

X in the repeating unit represented by formula (2-1) and / or formula (2-2) contained in the polyamic acid is a group represented by formula (X4), A is a group represented by formula (A6) Respectively.

Then, triethylamine (0.51 g, 0.005 mol) as an imidation catalyst was added to the polyamic acid solution Y all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C and the reaction was terminated by refluxing for 5 hours while distilling off the effluent from time to time. After cooling to room temperature to 120 ° C, N, N-dimethylacetamide g) was added and cooled with stirring to obtain an alicyclic polyimide resin solution (P2) having a solid content concentration of 20 mass%.

Preparation Example 3: Preparation of silicon 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 占 폚 and stirred with concentrated sulfuric acid g) was added slowly, and then water (3.3 g) was added dropwise over 1 hour. The mixture was stirred for 8 hours while maintaining the temperature at 10 to 20 占 폚, and then toluene was added thereto. Then, washing with water and separation of waste acid were carried out until the siloxane layer became neutral. The neutralized siloxane layer was heated and concentrated under reduced pressure to remove low boiling point fractions such as toluene to obtain organohydrogen siloxane A having k = 40 and l = 40 in the following formula (3).

1,3-divinyl-1,1,3,3-tetramethyldisiloxane (3.7 g), 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (41.4 g) and octamethylcyclotetrasiloxane (355.9 g) were added a silicate of potassium hydroxide in an amount of Si / K = 20,000 / 1 (molar ratio) and equilibrated in a nitrogen atmosphere at 150 DEG C for 6 hours. Ethylenechlorohydrin Was added in an amount of 2 moles per K, and neutralized at 120 DEG C for 2 hours. Thereafter, the resultant was subjected to heat bubbling treatment at 160 占 폚 and 666 Pa for 6 hours to cut off volatile components to obtain an alkenyl group-containing siloxane D having an alkenyl equivalent number La = 0.9 and Mw: 26,000 per 100 g.

The organohydrogensiloxane A and the alkenyl group-containing siloxane D were mixed so that the molar ratio of the total alkenyl groups and the total hydrogen atoms bonded to the silicon atoms (hydrogen atom / alkenyl group) was 0.9. 100 parts by mass of the siloxane mixture was mixed with 1 part by mass of a silicon compound having an acetylenic unsaturated group represented by the following formula (4) to obtain a platinum metal concentration of 100 ppm, and a platinum catalyst was added to 100 parts by mass of the resin component 5 parts by mass of heptane was added to obtain a silicone solution (P3) containing a crosslinkable organopolysiloxane.

≪ Example 1 >

First, the supporting substrate having a thickness of 0.5 mm was cleaned by pure water, and then UV-cleaned again.

Next, N, N-dimethylacetamide was added to the polyamic acid solution (P1), and the solid content concentration of the polyamic acid was diluted to 5 mass% to obtain Solution X. [ Solution X was coated on the first main surface of the supporting substrate with a spin coater (rotation speed: 2000 rpm, 15 seconds) to form a coating film containing polyamic acid on the supporting substrate (coating amount 2.0 g / m 2). In addition, the application amount of coating means the amount of polyamide acid remaining on the supporting substrate.

The polyamic acid is a resin obtained by reacting a compound represented by the formula (Y1) and a compound represented by the formula (B1).

Subsequently, the coating film was heated in the air at 60 占 폚 for 30 minutes and subsequently at 120 占 폚 for 30 minutes, and then the coating film was heated again at 350 占 폚 for 60 minutes to form a first polyimide resin layer (thickness: 0.1 占 퐉) . A polyimide resin having a repeating unit represented by the following formula (wherein X in formula (1) is a group represented by (X1), and A is a group represented by formula (A1) .

The imidization ratio of the polyimide resin in the first polyimide resin layer was 99.7%. The surface roughness Ra of the surface of the formed first polyimide resin layer was 0.8 nm.

Measurement of the imidization ratio and measurement of the surface roughness Ra were carried out by the above-mentioned method.

Subsequently, the glass substrate was washed with pure water and then UV-cleaned again.

Thereafter, the polyamic acid solution (P1) was coated on the first main surface of the glass substrate with a spin coater (rotation speed: 2000 rpm, 15 seconds) according to the same procedure as the method of forming the first polyimide resin layer, (Thickness: 5.0 占 퐉, Ra: 1.0 占 퐉) was formed on the second polyimide resin layer.

The imidization ratio of the polyimide resin in the second polyimide resin layer was 99.7%.

Thereafter, a supporting substrate having a resin layer including a supporting substrate and a first polyimide resin layer and a supporting substrate having a glass substrate and a second polyimide resin layer so as to contact the first polyimide resin layer and the second polyimide resin layer Were bonded to each other 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 air bubbles, no distortion defects, and good smoothness. The peel strength of the interface between the first polyimide resin layer and the second polyimide resin layer in the glass laminate S1 is determined by the peeling strength between the interface between the supporting substrate and the first polyimide resin layer, Was smaller than the peel strength at the interface of the mid resin layer.

Subsequently, the glass laminate S1 was subjected to heat treatment at 400 DEG C for 60 minutes in the atmosphere and then cooled to room temperature. As a result, separation of the supporting substrate of the glass laminate S1 and the glass substrate and separation of the first polyimide resin layer and the second poly The appearance of the mid resin layer such as foaming and whitening was not observed.

Then, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the first polyimide resin layer and the second polyimide resin layer at one of the four corner portions of the glass laminate S1 to form a notch portion of the peeling The vacuum adsorption pad is adsorbed to the surface of each of the glass substrate and the support substrate other than the release surface and water is sprayed to the interface between the first polyimide resin layer and the second polyimide resin layer, An external force was applied in a separating direction to separate the glass substrate and the supporting substrate without damaging them. Here, the insertion of the blade was carried out while spraying an antistatic fluid from an ionizer (manufactured by KEITH) to the interface.

Further, the first polyimide resin layer was separated with the supporting substrate, and the second polyimide resin layer was separated together with the glass substrate. From the above results, the peel strength of the interface between the first polyimide resin layer and the second polyimide resin layer was found to be higher than the peel strength of the interface between the supporting substrate and the first polyimide resin layer and the peeling strength between the glass substrate and the second polyimide resin layer It was confirmed that the peeling strength of the interface was smaller than that of the interface.

(Measurement of peel strength)

A peel test was conducted using the jig described in paragraph 0050 of Japanese Patent No. 5200538. The used jig is shown in Fig. The glass laminate S1 in Fig. 3 has a supporting substrate 12, a first polyimide resin layer 14a, a second polyimide resin layer 14b, and a glass substrate 16.

The glass laminate S1 was cut into a size of 50 mm in length x 50 mm in width and was laminated on both surfaces of the glass laminate S1 (supporting substrate 12 and glass substrate 16) And polycarbonate (60) having a thickness of 5 mm were bonded to each other with an epoxy two-liquid glass adhesive. Polycarbonate 70 having a length of 50 mm, a width of 50 mm, and a thickness of 5 mm was vertically joined again to the surfaces of the bonded polycarbonate 60 on both sides. As shown in Fig. 3, the position where the polycarbonate 70 is bonded is the position at the end of the polycarbonate 60 in the longitudinal direction and the position at the end of the polycarbonate 60 parallel to the side of the polycarbonate 60 .

The glass laminate S1 to which the polycarbonates 60 and 70 are bonded is provided so that the supporting substrate 12 is located on the lower side. The polycarbonate 70 adhered to the glass substrate 16 side was fixed with a jig and the polycarbonate 70 adhered to the supporting substrate 12 side was separated vertically down at a rate of 300 mm / On the other hand, when a force of 0.29 kg / cm 2 was applied, the first polyimide resin layer 14a and the second polyimide resin layer 14b were peeled off.

≪ Example 2 >

In the formation of the first polyimide resin layer, the polyamic acid solution (P1) was used in place of the solution X, the thickness of the first polyimide resin layer was changed from 0.1 탆 to 5.0 탆, and the thickness of the second polyimide resin layer Except that the solution X was used in place of the polyamic acid solution (P1) and the thickness of the second polyimide resin layer was changed from 5.0 m to 0.1 m in the formation of the glass laminate S2 .

The imidization rates of the polyimide resin in the first polyimide resin layer and the second polyimide resin layer were all 99.5%. The surface roughness Ra of the first polyimide resin layer and the second polyimide resin layer is shown in Table 1 described 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 air bubbles, no distortion defects, and good smoothness. The peel strength of the interface between the first polyimide resin layer and the second polyimide resin layer in the glass laminate S2 is preferably such that the peel strength of the interface between the support substrate and the first polyimide resin layer, Was smaller than the peel strength at the interface of the mid resin layer.

Subsequently, the glass laminate S2 was subjected to the same heat treatment as in Example 1, whereby the separation of the supporting substrate of the glass laminate S2 and the glass substrate and the separation of the first polyimide resin layer and the second polyimide resin layer, There was no change in appearance.

Then, with respect to the glass laminate S2, the supporting substrate and the glass substrate were separated in the same manner as in Example 1, and the glass substrate and the supporting substrate were separated without breakage.

Further, the first polyimide resin layer was separated with the supporting substrate, and the second polyimide resin layer was separated together with the glass substrate. From the above results, the peel strength of the interface between the first polyimide resin layer and the second polyimide resin layer was found to be higher than the peel strength of the interface between the supporting substrate and the first polyimide resin layer and the peeling strength between the glass substrate and the second polyimide resin layer It was confirmed that the peeling strength of the interface was smaller than that of the interface. Using the obtained glass laminate S2, the above (measurement of peel strength) was carried out. The results are shown in Table 1.

≪ Example 3 >

A glass laminate S3 was obtained in the same manner as in Example 1, except that the alicyclic polyimide resin solution (P2) was used instead of the polyamide acid solution (P1) at the time of forming the second polyimide resin layer.

Further, the second polyimide resin layer formed contains a polyimide resin in which X in the formula (1) contains a group represented by the formula (X4) and A contains a group represented by the formula (A6).

The imidization rates of the polyimide resin in the first polyimide resin layer and the second polyimide resin layer were all 99.5%. The surface roughness Ra of the first polyimide resin layer and the second polyimide resin layer is shown in Table 1 described 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, no distortion defects, and good smoothness. In the glass laminate S3, the peel strength of the interface between the first polyimide resin layer and the second polyimide resin layer is determined by the peel strength of the interface between the supporting substrate and the first polyimide resin layer, Was smaller than the peel strength at the interface of the mid resin layer.

Subsequently, the glass laminate S3 was subjected to the same heat treatment as in Example 1, whereby the separation of the supporting substrate of the glass laminate S3 and the glass substrate and the separation of the first polyimide resin layer and the second polyimide resin layer, And the like.

Then, the glass laminate S3 was separated from the glass substrate and the supporting substrate by the same method as in Example 1. As a result, the glass substrate and the supporting substrate were separated without breakage.

Further, the first polyimide resin layer was separated with the supporting substrate, and the second polyimide resin layer was separated together with the glass substrate. From the above results, the peel strength of the interface between the first polyimide resin layer and the second polyimide resin layer was found to be higher than the peel strength of the interface between the supporting substrate and the first polyimide resin layer and the peeling strength between the glass substrate and the second polyimide resin layer It was confirmed that the peeling strength of the interface was smaller than that of the interface. Using the obtained glass laminate S3, the above (measurement of peel strength) was carried out. The results are shown in Table 1.

≪ Comparative Example 1 &

The following polyamic acid solution (P4) was used in place of the solution X at the time of forming the first polyimide resin layer, the thickness of the first polyimide resin layer was changed from 0.1 mu m to 5.0 mu m, The procedure of Example 1 was repeated except that the solution X was used instead of the polyamide acid solution (P1) and the thickness of the second polyimide resin layer was changed from 5.0 占 퐉 to 0.1 占 퐉. An attempt was made to prepare the sieve C1.

The surface roughness Ra of the obtained first polyimide resin layer was 10.2 nm.

Further, as the method of adjusting the surface roughness Ra, the following treatment was carried out.

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 deteriorated, and desired glass laminate C1 could not be obtained.

(Polyamic acid solution (P4))

(DMAC-ST30, manufactured by Nissan Kagaku Kogyo Co., Ltd., average particle diameter 80 nm) in which colloidal silica was dispersed in dimethylacetamide was added to the polyamide acid solution (P1) obtained in Production Example 1, 1% by mass with respect to the total mass of the solution to obtain a polyamic acid solution (P4).

≪ Comparative Example 2 &

The first polyimide resin layer and the glass substrate were laminated in the same manner as in Example 2 without forming the second polyimide resin layer to form the supporting substrate, the first polyimide resin layer, and the glass substrate in this order To thereby produce a glass laminate C2.

When the supporting substrate and the glass substrate were separated from each other in the same manner as in Example 1 with respect to the obtained glass laminate C2, the first polyimide resin layer and the glass substrate were hardly peeled off. Using the obtained glass laminate C2, the above (measurement of peel strength) was carried out. The results are shown in Table 1.

≪ Comparative Example 3 &

The support substrate and the second polyimide resin layer were laminated in the same manner as in Example 1 without forming the first polyimide resin layer to form the support substrate, the second polyimide resin layer, and the glass substrate in this order To thereby produce a glass laminate C3.

When the supporting substrate and the glass substrate were separated from each other in the same manner as in Example 1 with respect to the obtained glass laminate C3, the second polyimide resin layer and the supporting substrate were hardly peeled off. Using the obtained glass laminate C3, the above (measurement of peel strength) was carried out. The results are shown in Table 1.

≪ Comparative Example 4 &

Except that the second polyimide resin layer was not formed using the silicon solution (P3) instead of the polyamic acid solution (P1) at the time of forming the first polyimide resin layer, a method similar to that of Example 1 To obtain a glass laminate C4 having a supporting substrate, a silicone resin layer and a glass substrate in this order. This embodiment corresponds to a mode using a silicone resin layer as a resin layer as described in Patent Document 1. [

The obtained glass laminate C4 was separated from the supporting substrate and the glass substrate by the same method as in Example 1. As a result, the silicon resin layer and the glass substrate were difficult to peel off and the silicon resin layer was cohesively broken and adhered to the glass substrate Together, the glass substrate broke. Using the obtained glass laminate C4, the above (measurement of peel strength) was carried out. The results are shown in Table 1.

Further, when the glass laminate C4 was heat-treated at 400 DEG C for 60 minutes in the atmosphere, the silicone resin layer was foamed or whitened.

The results of Examples 1 to 3 and Comparative Examples 1 to 4 are collectively shown in Table 1 below.

In the column "resin species" in Table 1, P1 is a resin obtained from Solution P1 of Production Example 1, and P2 is a resin obtained from Solution P2 of Production Example 2.

As shown in Table 1, in Examples 1 to 3 in which a predetermined resin layer was used, the adhesion at the time of lamination was excellent, and the decomposition of the resin layer was not observed even after the heat treatment at 400 DEG C for 1 hour. The peeling also 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 the first embodiment.

First, a silicon nitride film, a silicon oxide film, and an amorphous silicon film are formed in this order on the second main surface of the glass substrate in the glass laminate S1 by the plasma CVD method. Subsequently, low concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and dehydrogenation treatment is performed in a nitrogen atmosphere. Then, the amorphous silicon layer is crystallized by a laser annealing apparatus. Then, low-concentration phosphorus is injected into the amorphous silicon layer from an etching and ion-doping apparatus using a photolithography method to form N-type and P-type TFT areas. Subsequently, 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, and then molybdenum is formed by a sputtering method, and a gate electrode is formed by etching using a photolithography method . Then, a high concentration of boron and phosphorus are implanted into each of the N-type and P-type desired areas by a photolithography method and an ion doping apparatus to form a source area and a drain area. Subsequently, a TFT electrode is formed on the second main surface side of the glass substrate by the film formation of silicon oxide by the plasma CVD method, the interlayer insulating film by the sputtering method, and the aluminum film formation and the etching by the photolithography method. Subsequently, a hydrogenation treatment is performed in a hydrogen atmosphere, and then a passivation layer is formed by the film formation of nitrogen silicon by the plasma CVD method. Subsequently, a UV-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. Subsequently, indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.

Subsequently, 4, 4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injecting layer, and bis [(N-naphthyl (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene as a light emitting layer was added to an 8-quinolinol aluminum complex (Alq ₃ ) (BSN-BCN), and Alq ₃ as an electron transporting layer were formed in this order. [0100] Subsequently, aluminum was deposited by a sputtering method, and an aluminum film was formed by etching using photolithography Next, one glass substrate is further bonded and sealed on the second main surface side of the glass substrate via an adhesive layer of ultraviolet curing type, and the organic EL structure is formed on the glass substrate by the above procedure . A glass laminate S1 having an organic EL structure on a glass substrate (hereinafter referred to as panel A) Member for an electronic device.

Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the first polyimide resin layer and the second polyimide resin layer at the corners of the panel A after the sealing member side of the panel A was vacuum- And the interface between the polyimide resin layer and the second polyimide resin layer is imparted with a peeling moment. After the surface of the supporting substrate of the panel A is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the blade is carried out while spraying an antistatic fluid from the ionizer (manufactured by KYENS) onto the interface. Then, the vacuum adsorption pad is pulled up while water is sprayed on the peeling wire (front) while spraying the antistatic fluid continuously from the ionizer toward the formed voids. As a result, the supporting substrate having the resin layer can be peeled off, leaving only the glass substrate on which the organic EL structure is formed.

Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method, and is divided into a plurality of cells. Thereafter, the glass substrate on which the organic EL structure is formed and the counter substrate are assembled, And make them. The OLED thus obtained does not cause any problems in terms of characteristics.

&Lt; Example 5 >

In this example, an LCD is manufactured using the glass laminate S1 obtained in the first embodiment.

First, two pieces of glass laminate S1-1 and S1-2 were prepared, and on the second main surface of the glass substrate in one glass laminate S1-1, silicon nitride, silicon oxide, amorphous silicon The order is made in order. Subsequently, low-concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment. Then, the amorphous silicon layer is crystallized by a laser annealing apparatus. Then, low-concentration phosphorus is injected into the amorphous silicon layer from an etching and ion-doping apparatus using a photolithography method to form N-type and P-type TFT areas. Subsequently, 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, and then molybdenum is formed by a sputtering method, and a gate electrode is formed by etching using a photolithography method . Subsequently, boron and phosphorous of high concentration are implanted into desired areas of N type and P type respectively by photolithography and ion doping apparatus to form a source area and a drain area. Next, on the second main surface side of the glass substrate, an interlayer insulating film is formed by the silicon oxide film formation by the plasma CVD method, and a TFT electrode is formed by sputtering by aluminum film formation and etching by photolithography. Subsequently, a heat treatment is performed in a hydrogen atmosphere to perform a hydrogenation treatment, and then a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Subsequently, an ultraviolet curing 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. Subsequently, indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.

Subsequently, the other glass laminate S1-2 is heat-treated in an atmospheric environment. Subsequently, chromium is deposited on the second main surface of the glass substrate in the glass laminate S1-2 by sputtering, and the light shielding layer is formed by etching using photolithography. Then, a color resist is coated on the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by photolithography and thermal curing. Subsequently, indium tin oxide is formed by sputtering to form counter electrodes. Subsequently, an ultraviolet curable resin liquid is coated on the second main surface side of the glass substrate by a die coating method, and a columnar spacer is formed by photolithography and thermal curing. Then, a polyimide resin solution is applied by a roll coating method, an orientation layer is formed by thermal curing, and rubbing is performed.

Subsequently, the sealing resin liquid was drawn in a frame shape by the dispenser method, liquid crystal was dropped by the dispenser method in the frame, and then the glass laminate S1-1 on which the pixel electrode was formed was used to form two glass laminate The second main surface side of the glass substrate of the sieve S1 is bonded, and an LCD panel is obtained by ultraviolet curing and thermal curing.

Subsequently, the surface of the supporting substrate of the glass laminate S1-1 on the side opposite to the first polyimide resin layer side is vacuum-adsorbed on the surface of the base plate, so that the first polyimide resin layer at the corner of the glass laminate S1-2 and the second polyimide resin layer A stainless steel blade having a thickness of 0.1 mm is inserted into the interface of the polyimide resin layer to give a peeling moment to the interface between the first polyimide resin layer and the second polyimide resin layer. Here, the insertion of the blade is carried out while spraying an antistatic fluid from the ionizer (manufactured by KYENS) onto the interface. Subsequently, the vacuum adsorption pad is pulled up while water is being stuck in the peeling wire while the antistatic fluid is continuously sprayed from the ionizer toward the formed voids. After the second main surface of the supporting substrate of the glass laminate S1-2 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. As a result, the supporting substrate having the resin layer can be peeled off, leaving only empty cells of the LCD on which the supporting substrate of the glass laminate S1-1 is adhered.

Subsequently, a second main surface of the glass substrate on which the color filter was formed on the first main surface was vacuum-adsorbed on the surface of the base plate, and a thickness of 0.1 mm was formed at the interface between the first polyimide resin layer and the second polyimide resin layer at the corner of the glass laminate S1-1 Mm is inserted into the first polyimide resin layer and the second polyimide resin layer to give a moment of peeling to the interface between the first polyimide resin layer and the second polyimide resin layer. Then, the surface of the supporting substrate of the glass laminate S1-1 on the side opposite to the first polyimide resin layer side is adsorbed by the vacuum adsorption pad, and then the adsorption pad is raised while spraying water between the glass substrate and the resin layer . As a result, the supporting substrate having the resin layer can be separated while leaving only the LCD cell on the surface plate. In this manner, a plurality of LCD cells constituted by a glass substrate having a thickness of 0.1 mm are obtained.

Subsequently, the cells are divided into a plurality of LCD cells by a cutting process. A process of attaching a polarizing plate to each completed LCD cell is performed, and then a module forming process is performed to obtain an LCD. The LCD thus obtained does not cause a problem in terms of characteristics.

&Lt; Example 6 >

In this example, an OLED is manufactured by using the glass laminate S1 obtained in the first embodiment.

First, molybdenum is deposited on the second main surface of the glass substrate in the glass laminate S1 by the sputtering method, and the gate electrode is formed by etching using photolithography. Subsequently, aluminum oxide is formed on the second main surface side of the glass substrate by sputtering to further form a gate insulating film. Subsequently, indium gallium zinc oxide is formed by the sputtering method and the oxide semiconductor is etched by photolithography Layer. Subsequently, aluminum oxide is deposited on the second main surface side of the glass substrate by the sputtering method to further form a channel protective layer. Subsequently, molybdenum is deposited by sputtering and is etched by photolithography to form a source electrode and a drain electrode .

Subsequently, heat treatment is performed in the air. Subsequently, aluminum oxide is formed on the second main surface side of the glass substrate by sputtering to further form a passivation layer. Subsequently, indium tin oxide is formed by a sputtering method and a pixel electrode is formed by etching using a photolithography method do.

Subsequently, 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine was used as a hole injection layer on the second main surface side of the glass substrate by vapor deposition, and bis [(N-naphthyl) (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene-1-carboxylate was added to 8-quinolinol aluminum complex (Alq ₃ ) , And 5-dicarbononitrile (BSN-BCN) in an amount of 40% by volume, and Alq ₃ as an electron transporting layer were formed in this order. Subsequently, aluminum was deposited by a sputtering method and was subjected to etching by photolithography Next, one glass substrate is further bonded and sealed on the second main surface side of the glass substrate via an adhesive layer of ultraviolet curing type. [0053] By the above procedure, the organic EL structure is formed on the glass substrate. A glass laminate S1 having an organic EL structure on a substrate (hereinafter referred to as panel B) (A panel for a display device having a supporting substrate).

Subsequently, a stainless steel blade having a thickness of 0.1 mm was inserted into the interface between the first polyimide resin layer and the second polyimide resin layer at the corners of the panel B after the sealing member side of the panel B was vacuum- And the interface between the polyimide resin layer and the second polyimide resin layer is imparted with a peeling moment. After the surface of the supporting substrate of the panel B is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. Here, the insertion of the blade is carried out while spraying an antistatic fluid from the ionizer (manufactured by KYENS) onto the interface. Subsequently, the vacuum adsorption pad is pulled up while water is sprayed on the peeling wire while spraying the antistatic fluid continuously from the ionizer toward the formed voids. As a result, the supporting substrate having the resin layer can be peeled off, leaving only the glass substrate on which the organic EL structure is formed.

Subsequently, the separated glass substrate is cut using a laser cutter or a scribe-break method, and is divided into a plurality of cells. Thereafter, the glass substrate on which the organic EL structure is formed and the counter substrate are assembled, And make them. The OLED thus obtained does not cause any problems in terms of characteristics.

Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese Patent Application No. 2013-269304 filed on December 26, 2013, the contents of which are incorporated herein by reference.

10: Glass laminate
12: support substrate
14a: a first polyimide resin layer
14b: a second polyimide resin layer
16: glass substrate
18: Supporting substrate having a resin layer
20: glass substrate having a resin layer
22: member for electronic device
24: laminate having member for electronic device
26: Electronic device

Claims (5)

A support substrate having a support substrate and a resin layer having a layer of polyimide resin (first polyimide resin layer) formed on the support substrate, and a layer of a polyimide resin formed on the glass substrate and a second polyimide resin layer And a glass substrate having a resin layer having a surface layer
Wherein the first polyimide resin layer in the supporting substrate having the resin layer and the second polyimide resin layer in the glass substrate having the resin layer are in contact with each other so that the supporting substrate having the resin layer and the glass having the resin layer A substrate is stacked,
Wherein the surface roughness Ra of the surface of the first polyimide resin layer opposite to the side of the support substrate and the surface of the second polyimide resin layer opposite to the glass substrate side is 2.0 nm or less. The polyimide resin according to claim 1, wherein the polyimide resin comprises a repeating unit having a residue (X) of a tetracarboxylic acid and a residue (A) of a diamine represented by the following formula (1) The residue (A) of the diamine has at least one group selected from the group consisting of the following formulas (A1) to (X4), and the residue (X) A8). &Lt; / RTI &gt;

(Wherein X in the formula (1) represents a tetracarboxylic acid residue excluding a carboxyl group from a tetracarboxylic acid and A represents a diamine residue excluding an amino group from a diamine)

The method according to claim 2, wherein the residue (X) of the tetracarboxylic acid comprises at least one of a group represented by the formula (X1) and a group represented by the formula (X4) A group represented by the formula (A1) and a group represented by the formula (A6). The glass laminate according to any one of claims 1 to 3, wherein the supporting substrate is a glass plate. A member forming step of forming a member for an electronic device on a surface of the glass substrate in the glass laminate according to any one of claims 1 to 4 to obtain a laminate having an electronic device member,
And a separation step of removing the supporting substrate having the resin layer from the laminate having the electronic device member to obtain the electronic device having the second polyimide resin layer, the glass substrate, and the electronic device member, A method of manufacturing an electronic device.

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